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Heavy Metal Detection in Surface Water through Mesoporous
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Material
Research article
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Heavy Metal Detection in Surface Water
through Mesoporous Material
[Zeeshan Majeed Choudhary, Umaima riaz, nazia tabbasum, saba bashir, qazi abdul quddos]
[Zeeshan_majeed@hotmail.com]
Heavy Metal Detection in Surface Water
through Mesoporous Material
Abstract
In the present industrialized era, the solid wastes resulting from different industrialized processes
have imposed an extensive impact on water resources. The surface water is source of drinking
water for many people and the polluted water cannot thus harm the humans. The dumping of
disposal of solid wastes formed from different industrial processes thus is a serious issue that
should be addressed. The wastes consist of different toxicities including high level of heavy
metals that increase health burdens of society. There are different environmental problems that
have affected the world and amongst these, one of the serious environmental issues that have
obtained considerable importance in the present era is the heavy metal pollution of water. Thus
there is a crucial need to develop efficient analytical tools that can be used for monitoring of
heavy metals. The classical instrumental methods have been used from several years, but
presently optical chemical sensors are presented as effective alternative methods. The optical
chemical sensors use the mesoporous material that have some important characteristics such as
effective adsorption characteristic, morphology, geometry, high porosity, 3d shape that not leads
properties and response time. This is due to that intake of high quantity of heavy metals can
negatively affect different body parts and processes. This review study presents the
monitoring. With the advancement in mesoporous optical sensors that are silica based, a lot of
advantages in detecting heavy metals have been obtained. This review describes the evidences
1. INTRODUCTION
The people living in the areas near to industries are at higher risks to develop
complexities and thus industrial wastes should not be disposed in water. Thus the surface water
is analyzed by different ways for the detection of heavy metals, for instance copper, lead, iron
chromium etc. The porous materials used for detection are used with respect to different key
features such as analytical performance and sensitivity [1]. Silica is used for analytical detection
and reason is porous nature of silica and this reveals the importance of porosity as a predominant
factor for analyte diffusion in the pores that leads to easy detection. This is the reason that use of
mesoporous silica based material for detection process is high due to porous nature and well-
defined three dimensional structures. This review study is based on detection of heavy metals in
surface water through mesoporous material. Different studies conducted on the detection of
heavy metals in surface matters are used to determine the outcomes of different detection
The heavy metals monitoring in the water is described by the regulations to protect
environment and increase in the environmental awareness. The heavy metal is the term used for
the metals that have weight more than 5 g cm3. The prime source of these heavy metals is
different industrial processes. It is a matter of fact that most of these heavy metals are essential
nutrients for the healthy body, for instance iron, zinc, and copper; however, some of the high
metals are carcinogenic and toxic for the body, even if they are used in very small amounts or
traces, for instance, mercury, cadmium [2]. This is the reason that it is important to monitor the
heavy metal concentration in the environment. It is prior responsibility to control the harmful and
bioaccumulative properties of heavy metals. European Union legislation (EU) and World health
Organization (WHO) have provided the guidelines and the standards for monitoring the heavy
metals in water.
The identification of heavy metals in the water is carried out by using different advanced
inductively coupled plasma-mass spectrometry. These methods are very effective for
identification of heavy metals in water as the sensitivity and selectivity of these methods are very
high, but time intensive pre-treatment of sample, qualified and skilled staff and expensive
instrumentation for analysis are required [3]. On contrary to this, the potential of optical
chemical sensors (OCS) to detect the heavy metals in water is very high. These are the chemical
sensor groups where the analytical signal is generated in the transduction element with the use of
electromagnetic radiation. The interaction between the sample and radiation results in the
alteration in the specific optical parameters and thus, the analyte concentration can be calculated.
This type of sensor usually work on the principle of the organic dye or the immobilized indicator
that lead to some alteration in the optical characteristics, for example, emission, life time,
transmission and absorption after binding with the analyte in the water [1-3]. The OCS is
designed with the required properties of sensing and some of the important aspects related to this
aspect are the solid support, immobilization technique and suitable indicators [1-4]. The other
characteristics that should be considered are the suitable fictionalization and the morphological
characteristics of the materials. The determination of heavy metal ions, for instance zinc, copper,
mercury and many more has been enhanced with the introduction of advanced optical chemical
sensors that use the mesoporous silica. This review study is related to provide the critical review
of research studies that have described the importance of OCS for the identification of heavy
metals and the use of signal processing in this system [5]. This review also presents some
2. METHODOLOGY
This review study has used qualitative approach for conducting the research. A secondary
qualitative research design has been selected for performing this study because of the fact that
evidences from previous study are effective to describe the role of mesoporous materials for the
identification oif heavy metals in surface water and other liquids. This study is exploratory in
nature as it has explained the evidence and experimental based data from the other studies. For
this review, the gold standard databases are used for selection of appropriate research studies.
The reason for selecting this methodology is to provide in-depth understanding about different
mesoporous materials that are employed to describe the use of different mesoporus materials for
3. MESOPOROUS MATERIALS
From last two decades, the mesoporous materials are combined with the low emission
and absorption within visible spectra because of porous nature of mesoporous substances. This
combination is used as an efficient material for OCS that is used for detection of heavy metals in
water and nutrients. Mesoporous materials belong to nanostructure class which has well-defined
mesoscale with the pores of diameter ranging from 2-50nm and upto 1000m2/g surface area. The
formation of these mesostructured materials occur from the solution by the cross-linking and co-
assembly of inorganic species. These species form networks if the structure-directing agents are
present. According to the processing conditions and composition of the solution, the structure
directing agents usually block copolymer or surfactant self-organize into mesoscale structure
The inorganic mesoporous agents are available in different mesophase structures and the
examples are cage type cubic structure, 2D hexagonal structure, lamellar structure and many
other forms. The structural properties of mesoporous substances that are used for the heavy metal
detection in water are dependent on the surfactant geometries, the charges present on the head
group, the size of the group, molecular shape and saturation of the hydrophobic tails. There are
several types mesoporous silica materials that have been discovered and used from years in the
application of sensors. However, some of them are very important to be mentioned and these are
the MCM, HOM and SBA that are more effective than the other types. It is important to get a
view of the structure of different mesoprous substances that are used for the sensor application
and the effectiveness associated with each type of mesoporous material. MPS is used as a solid
support for the fabrication of the optical sensors and is associated with many advantages [7, 8].
MPS materials that are used for fabrication allow the covalent immobilizations by different
methods.
The first method by which the covalent immobilization may occur is the covalent
anchoring method of the active sensor dye at the process of synthesis and structure directing
agent removal with the help of low temperature. The other method of covalent immobilization is
the indicator dye grafting with the help of the photosynthetic functionalization making the
materials more effective and desirable for sensor application by minimizing the leaching. The
methods that are used for the immobilization of the indicators can be used for altering the
properties of sensor. The presence of high concentration of the dye molecules can result in the
self-quenching due to intermolecular collision as all molecules in the solution are free [9].
MPS are the mesoporous materials that have many pores and the silanol groups present
on the surface and this is the reason that the dye molecules are dispersed on the pore channels
and fixed at different location thus restricting the movement of dye to some areas. The self-
quenching nature of dye is not observed in the MPS as the high concentration of dye available as
immobilized can affect the detection limit and sensitivity of sensors by bringing the
improvement in signal to noise ratio. Thus the efficiency of these mesoprous materials is
improved and detection of heavy metals is enhanced. The other benefits that are associated with
the use of MPS and other mesoporous substances for the detection of heavy metals in water are
that it is possible to control the size of pores, tailor the inorganic framework and also can be a
source of improvement for the selectivity of the sensors [8, 10]. Moreover, the other advantages
that are associated with mesoporous materials are that the 3D geometry and shape of mesopore
has a significant impact on the response time and detection limit. The other important advantage
of using mesoporous materials for detection is that it can be prepared in different morphological;
forms and thus adsorption properties and limit of detection is also improved. The use of MPS
materials for optical sensing has been an important matter of study by different researchers.
According to review of different studies, mesoporous silica materials are effective to sense
different electrochemical and optical changes in the pH, toxic substances and relative humidity
[3, 6, 8, 10]. The review studies have also highlighted the environmental and biological
4. SENSING MECHANISM
One of the serious environmental issues that have obtained considerable importance in
the present era is the heavy metal pollution of water. Thus there is a crucial need to develop
efficient analytical tools that can be used for monitoring of heavy metals. The classical
instrumental methods have been used from several years, but presently optical chemical sensors
are presented as effective alternative methods. The optical chemical sensors use the mesoporous
material that have some important characteristics such as effective adsorption characteristic,
morphology, geometry, high porosity, 3d shape that not leads to improvement in limit of
detection but also bring effective improvement in selectivity properties and response time. This
review study presents the characteristics of mesoporous materials, sensing mechanisms of these
and benefits of continuous monitoring. With the advancement in mesoporous optical sensors that
are silica based, a lot of advantages in detecting heavy metals have been obtained [10, 11]. This
review describes the evidences from different research studies published on similar topic.
One of frequent method that is used for the optical sensing of heavy materials in water is
the use of mesoporous material related to the emission or absorption of light. Absorption of
sensing is carried out by the use of an indicator that leads to the change in the color when it made
the bonds with the analyte, thus make the visible changes. On the other hand, changes in
provided. Fluorescence and phosphorescence methods are more beneficial than the simple
absorption methods due to good specifications and sensitivities. The sensitivity of these methods
for detection of heavy metals is almost 1000 times good than the other methods. The review of
different studies has also revealed the emission intensity measurement is extensively used
because the required instrument is cheap. However some disadvantages are also associated with
this method because accuracy and precision of method is highly affected by even a minor change
in the intensity of light source, sensitivity of detector, concentration of indicator and thickness of
sensing layer [12]. There are some important approaches that can be used to reduce the problems
This technique is used for by the sensor that have a reference dye and prime benefits of
using the approach is the fluctuation in the excitation source and concentration of the sensor do
not affect the indicator and dye intensities. When the indicator based on fluorescent is used for
the detection of heavy metals and complexation is used for decreased or enhanced fluorescence.
The complexation of the process can be decreased by different factors. This mechanism is highly
acceptable for the detection of analytes. The sensors that use this method are efficient because
electron pair switch with the metal ion and transfer of electron is used for detection. Most of the
indicators have flurophore and ionophore. This is the reason that pct indicators shows the metal
ion complexation that leads to the metal in complexation [12-14]. Most of the studies have
highlighted that it is the better approach for the real samples of water for detection of heavy
metals and in case if effective indicator is used, the process gives better results.
5. CONTINUOUS MONITORING
This method is used for the monitoring of trace metal concentration in the water and
depends on the seasons, activities and different sources. The heavy metals monitoring, for
instance monitoring of cadmium, lead and copper for more than 4 days in the coastal water and
this has revealed that the concentration of different metals can be carried out in a time less than 1
hour[77]. The review of several studies has demonstrated that data from has confirmed the need
of the continuous monitoring. The determination of ion is carried out by the use of indicator dye
that lead7 to binding with different ions [15]. After the saturation of the metal ions, the increase
in the concentration of metal ions that can change the observed signal. Thus, there is an essential
The toxic heavy metal cation determination that is carried out by mesoporous sensor is
dependent on the process of incorporating dye molecules in mesoporous materials for method of
optical detection. The researchers of different studies have shown that most of the mesoporous
materials are used for the detection of copper and mercury. The other materials that are used for
the detection and sensing are lead, chromium, cobalt and zinc [12, 14, 16].
The sensing and mercury ion determination have described that it is an important topic
area of discussion for most researchers. With reference to mercury ion sensing material, the
commonly used element is SBA-15 and other materials that are used are HOM-9, UMV-7, and
Au-HMS and MPS nanoparticles. The mesoporous material that is used as an inorganic support
is UVM-7 is based on chemodosimeter principle. The reaction occurs by the attachment of the
material to SH group that are related to the silica framework. When the sensing material is added
to the solution that have mercury lead to the rapid change in the solution color because mercury
ions do a reaction with SH group, the colorless solution is changed to deep blue[84,81]. After
two minutes, filtration method is used for collection of solution and further the absorbance is
measured. It is possible to regenerate the inorganic support by washing the samples with HCl for
the quantitative removal of the mercury [17, 18]. Furthermore the dye leaching from inorganic
support has increased the need to understand practical application of mesoporous substance. In
which naked eye detection was used by the use of the mesoporous cubic discs and used to
Disc like sensors were used and immobilization of organic groups of two different kinds
occur and the first one is the tetraphenylprophine tetrasulphonic for the mercury ions and the use
of organic moiety to change the polarity of silica surface and prominent color change is observed
by the contact with analyte. The functionality of such system is retained even after a lot of reuse
cycle because CLO4 is used as decomplexation agent for this purpose [20-24]. After many reuse
cycle kinetic hindrance may occur and sensitivity remains almost 92% and it was possible to
reverse the disc. According to literature review of different studies, the sensing material that was
used in the process was light yellow solid that was changed to red color in 10seconds in case of
presence of mercury. EDTA was used to remove mercury ions. All these metals are considered
as effective for the determination of the mercury ions in the water and the assembling of SBA-15
and indicator dye is used for the determination of the mercury ions and these methods provide
quantitative results for the amount of mercury ions [25]. From the practical perspective, it is
Moreover, some of researchers have prepared silica based mesoporous sensors that are
worm like and efficiency of these sensors are described by several researchers as it has good
selectivity for mercury ion [26, 27]. The use of mesostructured silica that is core-shell shaped is
another efficient sensor for detection of mercury. Moreover, for sensing and identification of
mercury ions can be carried out by using MCM-41 mesoporous materials; however, the
efficiency of this material is lower than the other sensors that are used for detection of mercury
[28]. The determination of maximum level of mercury ion even in trace amount has become
element. The copper is required by the body because of physiological benefits associated with
copper and some of the important body functions that are required for the management of body
system. Thus, it is considered as an essential trace element but also a widespread pollutant
resulting in water pollution. There are different sensors that are utilized for sensing copper and
among the most important sensors; two are based on the principle of fluorescence quenching and
absorption resulting in the color changes [29, 30]. According to a research study, organic and
organic silica materials that are prepared by the receptor P2 immobilization in the channels of the
SBA-15 mesoporous silica materials has revealed the specific quenching response in water and
this detector is considered as highly sensitive for the copper ions and it is considered as the first
thing that is used for invivo detection of the copper ions[82]. The results have demonstrated that
MPS is found efficient study the bioactivity and toxicity of copper ions in the living organisms
[31, 32]. However, to characterize the characteristics f the sensor, it is important to carry out the
experiments on regeneration. There are some copper ion sensors that are currently developed and
silica[76]. When the copper ions bind with the dithizone, a blue shift is reflected by the
reflectance spectra associate with this sensor. The affinity of binding of metal-ligand and ion
diffusion is significantly affected by the geometries and shape of mesoporous materials. Despite
sensing the presence of active species, the sensors have a specific behavior related to geometry
that are mono-dispersed and are modified by anthracene derivatives with the fabrication with a
fluorescent sensor to determine the presence of copper ions in the water solution[78]. The sensor
that is used during the process is recovered by using a recovery agent that is EDTA in this
process. In the acidic condition, the identification of copper ion becomes very easy and the
changes are observed with the help of color changes of the solution from yellow to red within
few seconds[86]. In such processes EDTA is added as a regenerating agent so that sensor used in
this process can be reused and most of authors have presented the views that it possible to use
this material 6 times. The use of mesoporous material in the acidic condition can also be used for
the determination of mercury, cobalt, zinc, ferrous and cadmium ions. All of the above described
sensors are of high quality and can be used for identification of amount of copper ions in water to
present the quality and safety of water intended for drinking purpose [36-38].
The other heavy metals such as zinc, chromium, cobalt, lead and others can be identified with
the help of using mesoporous materials [40]. Ordered MPS material is used for determination of
zinc ions and this sensor have high selectivity, thus making the determination process efficient.
The presence of other heavy or light metals does not affect the identification of zinc ions.
Designing the diagnosis material by using physical absorption phenomenon can be used for
monitoring the presence of copper ions and hexagonal MPS is very efficient for this process [41].
The studies that have explained selectivity have described the importance of MPS materials and
reusing abilities. MPS can also be used for detection of other heavy metals. It is also imperative
to monitor cobalt ion because of its toxic properties that can produce harmful effects in the health
of people. SBA-15 has a high selectivity for chromium ions and modification of this sensor with
the help of dyes and surfactant can be used for detection of chromium ions [42,78].
The use of mesoporous silica based material for detection process of heavy metals in the
surface water is high due to porous nature and well-defined three dimensional structures of
mesoporous substances[79]. This review study has described the evidences for the application
and benefits that are associated with the implementation of mesoporous materials for the
detection of heavy metals in the water. The evidences from different studies conducted on the
detection of heavy metals in surface matters are used to determine the outcomes of different
detection methods and benefits of using mesoporous material in detection process. This study has
revealed that sensors and other instrumentation that are based on the use of mesoporous
substances are beneficial for the detection of heavy metals because of high degree of sensitivity
Well, If we talk about the comparison between the research of old times and that of today, the
vote ultimately goes to the new research according to methods that are utilized now a day. The
quality of the results is far better than the old methods that have been used by scientists since
long. The method of sensing by means of absorption and emission is quite old now. It has been
used since last century. The method has shown excellent results of sensing by the combination of
low absorption and emission. Calorimetric sensing has also been remained a common method of
the research in old days. The result is indicated by the color in this method. Despite of many
uses, these methods have many weak points like the time consuming and sometimes the results
are not up to the desired expectations. The mercury sensors are also in use by many researchers
and scientists. In calorimetric method, the color changes when the analyte is built up, the method
is commonly used because the change is not visible by microscope or any other such source but
can be viewed by naked eye. The mercury sensing and all other such techniques are still in use
by many countries. The modern research is going to replace the old one. The developed and the
developing countries are working on many projects and looking for the ways in order to have
more accurate and sensitive results. The PET mechanism is also excess in use and broadly
accepted by many experts. The decrease or increase in fluorescent light indicate the results. Now
a day, the electrochemical sensors and the cathode modified sensors are capturing the attention
of researchers. These methods are the result of modern research and provide more accurate
results than those of previous methods. There are many advantages of these research methods.
The electrochemical devices are easy to use and easy to handle for the new comers in the field.
The X-ray fluorescence, neutron spectroscopy and all such methods are still in use but due to
more chances of error, these are avoided now a day. The modern research methods like the
electrochemical and modified cathode methods are cheap, less expensive and have easy access to
public. These methods give fast experimental analysis and real time results, on this basis these
methods are more reliable and more effective to use. The use of MPS material is a common
method in both old and new research study. All the old methods of research study are must costly
and expensive methods and can be used only in the developed states. All the researchers and
scientists can not have the approach to those methods. The major draw backs are the proper
training and the experts are needed to operate the machinery and to process the whole procedure.
No doubt, those methods were unique and have used for the successful determination of the
required results but these draw backs lead the electrochemical system to replace them. The
modern methods can easily be operated by all the users and are cheap. This is the brief
It is evident from different studies that the use of mesoporous materials for the detection
of heavy metals in the water provides better outcomes as compared to the use of other materials
for detection. Moreover, the mesoporous materials that are used to increase the intensity of
detection of heavy metals are available in different sizes and shapes and the chemical physical
properties also varied and thus can be used for the analysis of water and detection of heavy
metals. The sensing of heavy metal ions in the water is most frequently carried out by using
HOM mesoporous, MCM-41 and SBA-15. Some studies have also presented the application of
the disordered materials that are worm-like for detecting heavy metals. The sensors that are used
for detection are not present in the form of thin films but are present as particles. Most of the
published evidence based studies have considered the determination of mercury in the surface
water as it is identified as most toxic contaminants for the environment. MCM-41, SBA-15 and
HOM are described as the most commonly used solid supports for sensing of the heavy metals in
the water. In order to determine the mercury in water, the most commonly used mesoporous
material is SBA-15 and HOM which is a 3D material is suitable in terms of sensitivity and time.
The application of the physical entrapment of dye for sensing and detecting the heavy
metals in water has revealed that no leaching of the indicators has occurred and thus, the stability
results obtained for the sample are good. The analysis of water was good achieved with the use
of MPS-based sensors that have good selectivity. Moreover, the loss on dryness (LOD) is
lowered adsorption characteristics of the heavy metals. The mesoporous materials are considered
as effective for the detection of different heavy metals that can be harmful for the health and can
lead to environmental losses. The sensitive technique is fluorescence in contrast to
spectrophotometry and the absorption with the fluorescence-based techniques with MPS based
sensors is more.
The surface water either it is river water or the waste water consists of different
biological and chemical species that can interfere the sensing signals. Thus, the real world
samples are required to be used to describe the practical application of mesoporous silica-based
sensors. Most of the research studies related to the identification of heavy metals in water with
the use of mesoporous materials have described the importance of these materials in the
detection of heavy metals. Most of the studies have reported the detection of heavy metals in
organic water solution and only few of them have considered the testing of real world samples.
There are only few research studies that have described the validation of sensors data and no
study has highlighted the MPS based sensors that can be used for detection of nickel and
cadmium despite the fact that water framework directives are considered as priority targets in the
detection of heavy metals in water. Thus, it can be concluded that use of sensors that are based
on the mesoporous materials is an effective technique for detection of heavy metals in water;
however, further advancement is required to develop the implementation of this technique for
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