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Heavy Metal Detection in Surface Water through Mesoporous

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Research article

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Zeeshan Majeed Choudhary

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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]

[JINNAH MEDICAL AND DENTAL COLLEGE KARACHI ]

[KARACHI UNIVESITY KARACHI ]

[30TH MARCH 2017]

[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

to improvement in limit of detection but also bring effective improvement in selectivity

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

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. This review describes the evidences

from different research studies published on similar topic.

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

methods and benefits of using mesoporous material in detection process.

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

techniques, for example, X-ray fluorescence spectroscopy, Atomic absorption spectroscopy,

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

important characteristics and application of the mesoporous materials.

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

identification of mercury, copper, zinc and other heavy metals.

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

ranging from 2-50nm in diameter [6].

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

implementation of these mesoporous materials.

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

emission characteristics are reported in the emission when an electromagnetic wavelength is

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

is to use the ratimetric measurements.

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

need of continuous monitoring of the process as described by various studies.

6. USE OF SPECIFIC SENSOR FOR DETECTION OF HEAVY METAL IONS

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].

6.1. Detection and Sensing of Mercury

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

remove mercury ions from the water samples [19].

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

required to consider the detection limit and sensitivity of the device.

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

possible because of the use of mesoporous materials as the sensors.


6.2. Sensing of Copper

If the integrity of water is considered an important ion of consideration is copper because

it is imperative to control the quantity of copper throughout the processes as it is important

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

based on dithizone in 2Dhexagonal MCM and cubic 3D HOM-II monoliths of mesoporous

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

and 3D shape and a specific behavior is exhibited by these sensors [33-35].


On contrary to this, some of the researchers have used the mesoporous silica nanospores

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].

6.3.Sensing Other heavy metals

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

and sestivity of these materials in detection [43, 44].

7. Comparison between old and new research

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

comparison between old and the new research study.


8. Conclusion

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

detection of other heavy metals that are ignored.


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