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TOOLS, TECHNIQUES
AND PROTOCOLS
FOR MONITORING
ENVIRONMENTAL
CONTAMINANTS
TOOLS, TECHNIQUES
AND PROTOCOLS
FOR MONITORING
ENVIRONMENTAL
CONTAMINANTS
Edited by

SATINDER KAUR BRAR

KRISHNAMOORTHY HEGDE
VINAYAK LAXMAN PACHAPUR
Elsevier
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Contributors

Bal Ram Adhikari

Laboratory of Biosensors and Nanomachines, Department of Chemistry, University of Montreal,
Montreal, QC, Canada

Shadab Ahmed
Institute of Bioinformatics and Biotechnology, Savitribai Phule Pune University (Formerly
University of Pune), Pune, India

V. Amrutha
Electronics and Communication Engineering, National Institute of Technology Rourkela,
Rourkela, India

Antonio Avalos-Ramı́rez
National Center in Environmental Technology and Electrochemistry, Shawinigan, QC, Canada

Raj Mohan Balakrishnan

Department of Chemical Engineering, National Institute of Technology, Surathkal, India

Fatima Bendourou
INRS-ETE, University of Quebec, Quebec, QC, Canada

Satinder Kaur Brar

INRS-ETE, University of Quebec, Quebec, QC, Canada

Mona Chaali
INRS-ETE, University of Quebec, Quebec, QC, Canada

Jiping Chen
CAS Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of
Chemical Physics, Chinese Academy of Sciences, Dalian, People’s Republic of China

Agnieszka Cuprys
INRS-ETE, University of Quebec, Quebec, QC, Canada

Achlesh Daverey
School of Environment and Natural Resources, Doon University, Dehradun, India

Beatriz Delgado-Cano
National Center in Environmental Technology and Electrochemistry, Shawinigan, QC, Canada

Dhanjai
Department of Mathematical and Physical Sciences, Concordia University of Edmonton;
Department of Physical Sciences, MacEwan University, Edmonton, AB, Canada; CAS Key

xiii
xiv Contributors

Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences, Dalian, People’s Republic of China

Dhruba Dhar
Department of Bio-Engineering, Birla Institute of Technology, Mesra, Ranchi, India

Kasturi Dutta
Department of Biotechnology and Medical Engineering, National Institute of Technology
Rourkela, Rourkela, India

Rosa Galvez-Cloutier
Universite Laval, Department of Civil Engineering and Water Engineering, Quebec, QC,
Canada

Laura Gatel
INRS-ETE, University of Quebec, Quebec, QC, Canada

Natali Gómez-Falcón
Higher Technological Institute of Tierra Blanca (ITSTB), Tierra Blanca, Veracruz, Mexico

Krishnamoorthy Hegde
INRS-ETE, University of Quebec, Quebec, QC, Canada

Ka Lok Hong
Wilkes University, Wilkes-Barre, PA, United States

Rekha Jain
Department of Microbiology, Marwadi University, Rajkot, India

Guneet Kaur
Department of Biology, Hong Kong Baptist University, Kowloon Tong, Hong Kong

Gagandeep Kaur
Biosensor Technology Laboratory, Department of Biotechnology, Punjabi University, Patiala,
India

Pratik Kumar
INRS-ETE, University of Quebec, Quebec, QC, Canada

Xianbo Lu
CAS Key Laboratory of Separation Science for Analytical Chemistry, Dalian
Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, People’s
Republic of China

Samrat Maratkar
Institute of Bioinformatics and Biotechnology, Savitribai Phule Pune University (Formerly
University of Pune), Pune, India

Araceli Dalila Larios Martı́nez

INRS-ETE, University of Quebec, Quebec, QC, Canada
 Contributors xv

Saba Miri
INRS-ETE, University of Quebec, Quebec, QC, Canada

Samuel M. Mugo
Department of Physical Sciences, MacEwan University, Edmonton, AB, Canada

Vinod Kumar Nigam

Department of Bio-Engineering, Birla Institute of Technology, Mesra, Ranchi, India

Carlos S. Osorio-González
INRS-ETE, University of Quebec, Quebec, QC, Canada

Preetika Kuknur Pachapur

INRS-ETE, University of Quebec, Quebec, QC, Canada

Vinayak Laxman Pachapur

INRS-ETE, University of Quebec; Department of Civil Engineering and Water Engineering,
Laval University, Quebec, QC, Canada

Vishal Pandey
Institute of Bioinformatics and Biotechnology, Savitribai Phule Pune University (Formerly
University of Pune), Pune, India

Nachiket Pathak
Institute of Bioinformatics and Biotechnology, Savitribai Phule Pune University (Formerly
University of Pune), Pune, India

Rama Pulicharla
INRS-ETE, University of Quebec, Quebec, QC, Canada

Keyur Raval
Department of Chemical Engineering, National Institute of Technology, Surathkal, India

Ritu Raval
Department of Biotechnology, Manipal Institute of Technology, MAHE, Manipal, India

Shounak Roy
BioX Centre and School of Basic Sciences, Indian Institute of Technology Mandi, Himachal
Pradesh, India

Rahul Saini
INRS-ETE, University of Quebec, Quebec, QC, Canada

Angana Sarkar
Department of Biotechnology and Medical Engineering, National Institute of Technology
Rourkela, Rourkela, India

Kuntal Deb Sarkar

Electronics and Communication Engineering, National Institute of Technology Rourkela,
Rourkela, India
xvi Contributors

Santanu Sasidharan
Department of Biotechnology, National Institute of Technology, Warangal, India

Prakash Saudagar
Department of Biotechnology, National Institute of Technology, Warangal, India

Naeem Shaikh
Institute of Bioinformatics and Biotechnology, Savitribai Phule Pune University (Formerly
University of Pune), Pune, India

Sujata Sinha
Department of Biochemical Engineering and Biotechnology, Indian Institute of Technology
Delhi, New Delhi, India

Ankita Sinha
Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education,
China), School of Environmental Science and Technology, Dalian University of Technology,
Dalian, People’s Republic of China

Akshay Sonawane
Institute of Bioinformatics and Biotechnology, Savitribai Phule Pune University (Formerly
University of Pune), Pune, India

Niranjan Suralikerimath
INRS-ETE, University of Quebec, Quebec, QC, Canada

Gayatri Suresh
INRS-ETE, University of Quebec, Quebec, QC, Canada

Priyanka Uddandarao
Department of Chemical Engineering, National Institute of Technology, Surathkal, India

Neelam Verma
Division of Research and Development, Lovely Professional University, Phagwara; Biosensor
Technology Laboratory, Department of Biotechnology, Punjabi University, Patiala, India

Mausam Verma
CO2 Solutions Inc., Quebec, QC, Canada
CHAPTER 1

An overview of analytical
methodologies for environmental
monitoring
Achlesh
*
Daverey*, Kasturi Dutta†, Angana Sarkar†
School of Environment and Natural Resources, Doon University, Dehradun, India
†
Department of Biotechnology and Medical Engineering, National Institute of Technology Rourkela, Rourkela, India

Contents
1. Introduction 3
2. Conventional techniques for the detection, identification, and quantification of ECs 6
2.1 Chromatography-based methods 6
2.2 Immunochemical techniques 9
3. Biosensors for the detection, identification, and quantification of ECs 9
3.1 Aptasensors for detection of emerging contaminants 10
3.2 Enzyme and whole cell biosensors 11
3.3 Immunosensors 11
3.4 Molecularly imprinted polymer (MIP) biosensors 11
3.5 Nanomaterial-based biosensors 12
4. Conclusion 13
References 13

1. Introduction
Emerging contaminants (ECs) or emerging pollutants (EPs) or Contaminants of emerg-
ing concern (CEC) are defined as synthetic or naturally occurring substances or chemicals
that are not included in routine environmental monitoring programs but have the poten-
tial to enter the environment and cause known or suspected adverse ecological and (or)
human health effects. Such substances have no regulatory standards (few countries now
have) but may be candidate for future legislation depending on their ecotoxicity, poten-
tial health effects, public perception, and frequency of occurrence in the environment [1].
Occurrence of these candidates in the environment has been either discovered recently
due to the advancements in the analytical tools and techniques or their environmental
presence and significance are only now being evaluated. ECs include a wide range of
chemicals, such as persistent organic pollutants, pharmaceuticals and personal care prod-
ucts (PPCPs), endocrine disrupting compounds (EDCs), nanomaterials [1]. As on Feb-
ruary 2016, Norman [2] has compiled a list of more than 1000 ECs, which include
surfactants, PPCPs, flame retardants, gasoline additives and their degradation products,

Tools, Techniques and Protocols for Monitoring Environmental Contaminants Copyright © 2019 Elsevier Inc.
https://doi.org/10.1016/B978-0-12-814679-8.00001-7 All rights reserved. 3
4 Tools, techniques and protocols for monitoring environmental contaminants

biocides, pesticides and their degradation products, and various proven or suspected
EDCs. Table 1.1 presents common classes of ECs along with their examples and known
adverse environmental effects.
Limited information is available in literature on the fate of these broad ranges of ECs
and their environmental effects at the trace levels. This limits the policy makers to draft
regulations for the long-term impact assessment due to exposure of ECs at low levels.
Therefore it is imperative to analyze and monitor the concentrations of these ECs at
the emission source as well as within the different environmental matrices or compart-
ments (water, air, and soil) for better understanding of their long-term impact assessment
[12]. Analysis of ECs is not an easy task as [5]:
(a) Environmental matrices are very complex in nature.
(b) ECs are usually present in very low levels (ppt to ppb) in environmental systems.
(c) Multiple isomers/enantiomers/diastereomers or analogs of ECs are present in envi-
ronmental systems.
(d) ECs are “emerging” in nature, that is recently identified in the environment and
lacks analytical methods for proper identification and quantification.
Conventional analytical techniques are available to detect the ECs and their possible
metabolites in different environment. However, such analytical techniques are time

Table 1.1 Classification of emerging pollutants with typical examples and associated effects

Known environmental
Class Example effects References
Endocrine Phthalates (octylphenols, • Interferes with nor- [3]
disrupting nonylphenols, di(2- mal process of natu-
chemicals ethylhexyl) phthalate ral bloodborne
(DEHP)) hormones
Bisphenol A; polychlorinated • Effect reproductive
biphenyls (PCBs) functions
Dioxins • Effect central ner-
vous system
Pharmaceuticals Antibiotics (tetracycline, • Antibiotic resistance [4, 5]
erythromycin); steroids and in the environment
hormones; nonsteroidal • Poisoning to birds
antiinflammatory drugs and animals
(NSAIDs) (Diclofenac poison-
ing to vultures)
Pesticides and Fipronil; permethrin; • Possible carcinogen [6, 7]
insecticides fenitrothion; Bacillus • Highly toxic to liz-
thuringiensis israelensis ard, bees, gallina-
ceous birds
• Endocrine
disruption
 An overview of analytical methodologies for environmental monitoring 5

Table 1.1 Classification of emerging pollutants with typical examples and associated effects—cont’d

Known environmental
Class Example effects References
Personal care Fragrances (nitro, polycyclic and • Bacterial resistance [8, 9]
products macrocyclic musks, • Endocrine
phthalates) disruption
Sunscreen agents • Increased risk of
(benzophenone, cancer
methylbenzylidene camphor)
Insect repellants (N,N-
diethyl-m-toluamide
(DEET));
parahydroxybenzoates
Flame Organophosphate esters • Endocrine [3, 5–7,
retardants (chlorinated tri(2-chloroethyl) disruption 10]
and phosphate; and • Indications of
plasticizers tri(chloropropyl) phosphate; increased risk for
tributyl phosphate); cancer
polybrominated diphenyl • Meiotic aneuploidy
ethers; tetrabromobisphenol and synaptic
A; bisphenol A • Abnormalities in
animals
• Estrogenic and
reproductive effects
in birds
Industrial Bisphenol A; alkyl phenols; • Endocrine [3, 5, 6]
additives phthalate esters disruption
Chelating agents (EDTA), • Can be toxic to ani-
aromatic sulfonates mals, ecosystems,
and humans
Hormones and Estradiol, estrone, estriol, • Endocrine [9]
steroids diethylstilbestrol (DES) disruption
Surfactants and Alkylphenol ethoxylates, Possible endocrine [6, 9]
their 4-nonylphnol disruptive effect
metabolites 4-Octylphenol, alkylphenol Possible toxicity to
carboxylates; sodium lauryl animals and aquatic
sulfates species
Nanomaterials Carbon nanotubes; nanowires; Ecotoxicity effects are [11]
TiO2, ZnO, iron oxides, at immature state
hydroxyapatite, and metallic
nanoparticles
6 Tools, techniques and protocols for monitoring environmental contaminants

consuming, monitor pollutant offline, and require sophisticated and costly instruments.
Therefore a lot of efforts have been made to develop biosensor-based analytical tech-
niques, which are less expensive, quick, and have very low detection limits for online
monitoring of ECs in the environment. The following sections discuss various tech-
niques (conventional as well as biosensor based) available for the detection, identification,
and quantification of ECs along with their advantages and limitations.

2. Conventional techniques for the detection, identification,

and quantification of ECs
2.1 Chromatography-based methods
Chromatography-based separation techniques such as Gas Chromatography (GC) and
Liquid Chromatography (LC) coupled with Mass spectrometer (MS) are the conven-
tional and most frequently applied tools for the detection, identification, and quantifica-
tion of ECs in the environment. There are various factors which determine the use of
either GC or LC for the analysis of ECs in different environmental matrices. GC is advan-
tageous because of its faster analysis and better separation efficiency than LC [13].
However, the most important characteristics of pollutant (analyte) to be analyzed by
GC are volatility and stability at higher temperature. Therefore GC is the best tool to
analyze the volatile pollutant [14].

2.1.1 GC and GC-MS

The application of conventional GC (one-dimensional GC or 1D GC) is limited to the
analysis of mixtures having 50–60 pollutants [15]. Also, 1D GC is not able to separate
the mixture of hydrocarbons (>C10) [16]. These issues of 1D GC have been resolved
by the development of multidimensional GC such as 2D GC (GC  GC). In 2D
GC, two columns (in general nonpolar primary column followed by polar secondary col-
umn) are sequentially connected, which enhance the peak capacity and separation power
of the instrument [16]. High-end multidimensional GC systems use 2D GC (GC  GC)
coupled with MS and can be used for the analysis of highly complex samples [13].
Sample pretreatment such as extraction of pollutant from environmental matrices is
prerequisite for the chromatographic identification and analyses of ECs. There are var-
ious techniques such as solid-phase extraction (SPE), liquid-liquid micro-extraction
(LLME), and microwave-assisted extraction (MAE) for the extraction of pollutant from
the environmental matrices [17]. SPE method prior to GC-MS analyses for the screening
of ECs such as neutral and acidic pharmaceuticals, bisphenol A and their chlorinated
derivatives, endocrine disrupting phenolic compounds and steroids in water, and waste-
water samples has been most extensively used by the researchers around the world
[17–20]. Kotowska et al. [21] identified 120 compounds including drug remnants such
as ibuprofen, naproxen, and caffeine from wastewater sample. Antoniou et al. [22]
 An overview of analytical methodologies for environmental monitoring 7

developed a solid-phase micro-extraction (SPME) method as pretreatment technique for

the extraction of PPCPs and EDCs from the wastewater treatment plant effluents and
analyzed these ECs by GC-MS. The developed method by the authors is simple, solvent
free, and low cost. However, the analysis time (extraction procedure and GC-MS anal-
ysis) reported by the authors is about 2 h. Graphene, a carbon nanomaterial due to its high
surface area has been used as adsorbent matrix in SPE for the analysis of PPCPs in waste-
water samples by GC-MS [23]. Up to 87.6% recovery of the analyte has been reported by
using the graphene-based SPE. Ultrasound-assisted extraction has also been used as a
low-cost method for the extraction of ECs from the environmental samples [17, 24].
The extraction time (5–45 min) and solvent consumption in ultrasound-assisted extrac-
tion are lower than the classical techniques [24]. Recently, ultrasound-assisted extraction
is combined with SPME coupled with GC-MS for the analysis of PPCPs in river sedi-
ments [24]. Combination of ultrasound-assisted extraction and SPME integrates multiple
steps, that is, extraction, cleaning, isolation, and enrichment of analytes in a miniaturized
system, which required very small amount of sample (mL) with limits of detection and
quantification of PPCPs <0.25 ng/g and <0.8 ng/g, respectively, in river sediment [24].
Polar ECs are less volatile and therefore, derivatization is necessary to analyze them by
GC. Derivatization reduces the polarity and enhances the volatility of polar EC by con-
verting polar groups into less polar moieties [25, 26]. This step enhances the separation,
selectivity, and sensitivity of the polar contaminant by GC [27]. However, this additional
derivatization step in the analysis of polar ECs by GC-MS is time consuming, tedious,
laborious, and uses highly toxic and carcinogenic chemicals such as diazomethane for
derivatization of chlorinated phenoxy acid herbicides. Moreover, chances of sample con-
tamination increase during derivatization [28]. Furthermore, temperature-sensitive ECs
cannot be analyzed by GC-based techniques.

2.1.2 LC and LC-MS

LC systems are the preferred over GC-based techniques for the analysis of polar and
temperature-sensitive ECs in different environmental matrices. However, the analysis
of pollutants by LC-based techniques is more time consuming than GC-based tech-
niques. Therefore LC systems have been upgraded in the recent past through modern
approaches in order to achieve the fast separation of ECs while maintaining the high res-
olution and separation efficiency. Ultra-high-pressure LC (UHPLC) uses columns
packed with <2 μm particles (sub-2 μm particles packed columns) compared to conven-
tional high-pressure LC (HPLC) columns having 5 or 3 μm particles. Advantages of
UHPLC over conventional HPLC include: (1) lesser amount of solvents required for
sample elution, (2) much narrower and concentrated bands are obtained, and (3) sepa-
ration speed increases up to ninefold [29, 30]. The best part of UHPLC-MS system is very
quick (<5 min) separation of target compound with quantification range of 10–50 ng/L
[31]. Due to these advantages, UHPLC is one of the most promising analytical tools for
8 Tools, techniques and protocols for monitoring environmental contaminants

the analysis and multiresidue screening of organic ECs in environmental matrices [32].
For example, analysis of antibiotic residues and their metabolites, drugs of abuse and their
metabolites in urban wastewater and surface water [33, 34] and pesticides in wastewater
have been detected and analyzed by UHPLC [35]. UHPLC coupled with MS (UHPLC-
MS systems) is efficient in screening of suspect and nontarget ECs in water samples [36,
37]. However, the main drawback of UHPLC system is increase in backpressure (up to
27-fold) and therefore, a special hardware is required to handle this high pressure, which
increases the cost of LC system [31, 38].
Core-shell columns or fused-core columns in place of sub-2 μm particles packed col-
umns are used in LC systems to overcome the high backpressure issue of UHPLC. Core-
shell columns use superficially porous particles, which enable high-speed analysis while
maintaining the high separation efficiency equivalent to UHPLC without increasing the
backpressure. Applications of LC systems using fused-core columns for analysis of Ecs
such as pharmaceuticals (illicit drugs, psychiatric drugs, and selected human metabolites,
etc.), bisphenol A and their metabolites in wastewater and drinking water [39–42], naph-
thenic acids in surface waters [43], and polar pesticides and its degradation products and
some nitro-phenols in rainwater [44] are available in literature.
Development of automated instruments such as online SPE coupled to LC and MS
(SPE-LC-MS or SPE-LC-MS/MS) is another advancement in LC. Such automated
instruments integrate three steps—extraction, purification, and detection and have
user-friendly advanced integrated LC-MS control software and require small sample vol-
ume (as low as 1 mL) [32, 45]. Therefore automated instruments are highly recommended
when sample volume is very low. SPE-LC-MS or SPE-LC-MS/MS techniques have
become more and more popular in the recent past for the detection and determination
of EC [46, 47]. For example, Wode et al. [48] used a multiresidue analytical method
for the simultaneous determination of 72 ECs (industrial chemicals, pharmaceuticals,
psychoactive substances, flame retardants, neutral and acidic pesticides) in water samples
with UHPLC-MS. Recently, an automated online SPE coupled to LC-tandem mass
spectrometry (SPE-LC-MS/MS) has been used by Anumol and Snyder [46] for the rapid
analysis of trace organic compounds such as pharmaceuticals, PCPs, hormones, and pes-
ticides in water. The authors used polymeric reversed-phase cartridges in SPE-LC-MS/
MS. Gorga et al. [47, 49] analyzed endocrine disrupters and related compounds in various
environmental matrixes (river, sediments, wastewater, and sewage sludge).
Despite the advancements in the tools and techniques and accuracy and sensitivity,
chromatographic methods (LC-MS and GC-MS) have the following limitations [50, 51]:
1. They are not suitable for on-site and continuous analysis of EC.
2. These methods are limited to centralized high-end laboratories.
3. Instrumentation systems are very costly.
4. Overall analysis (including sample pretreatment) of ECs is time consuming.
5. Highly skilled and trained personnel is needed to use these methods.
 An overview of analytical methodologies for environmental monitoring 9

2.2 Immunochemical techniques

Immunochemical techniques such as enzyme-linked immunosorbent assays (ELISA) and
time-resolved fluoroimmunoassay (TRFIA) have also been developed for the detection
and quantification of ECs such as EDC from the environmental matrices [52–56]. ELISA
is based on the principle of antigen-antibody interaction, while TRFIA is based on the
fluorescence properties of the lanthanide ions [56]. TRFIA is ultrasensitive than ELISA
but lanthanide ions used in TRFIA are very costly, which discourage its use over ELISA.
Immunochemical techniques are advantageous over chromatographic techniques due to
their fast analysis time, selectivity, sensitivity, reliability, simplicity (simple or no sample
pretreatment), and low sample volume [56]. However, the limitations or drawbacks of
immunochemical techniques are [57] as follows:
1. Biological materials (antibody) used in the immunochemical techniques are less stable.
2. Assay procedure is complicated and have multisteps.
3. Highly skilled person is required for preparation of antibody and analysis.
4. Difficult to use on-site.

3. Biosensors for the detection, identification, and quantification of ECs

Biosensor is defined as “a device that uses specific biochemical reactions mediated by iso-
lated enzymes, immunosystems, tissues, organelles or whole cells to detect chemical com-
pounds usually by electrical, thermal or optical signals” by the International Union of
Pure and Applied Chemistry (IUPAC) [57]. In other words, biosensors sense the signals
produced by the bio/chemical reactions involving the analyte. These signals are propor-
tional to the concentration of the analyte in the reaction mixture [58]. The biosensors are
gaining lot of attention in the screening and detection of ECs in the environmental matri-
ces due to their selectivity, reproducibility, stability, sensitivity, portability, miniaturiza-
tion, on-site monitoring and enable permanent and unattended operation in the field
[57–59]. The biomonitoring of ECs by using biosensors is another advantage over
GC-LC-based systems. Determination of eco-effects (cytotoxicity, genotoxicity, endo-
crine disrupting effects, etc.) of environmental contaminants is feasible by biosensors [57].
Justino et al. [60] summarized the recent applications of different biosensors in environ-
mental monitoring of ECs such as pesticides (including organophosphorous pesticides),
pathogens, and endocrine disrupting chemicals. The limit of detection of biosensors was
reported to be up to ppb levels [60].
A typical biosensor has the following main components: analyte (the pollutant), bior-
eceptor (recognize the analyte through biochemical reactions and produces signals),
transducer (convert biochemical signals to electronic signals), and display. Biosensors
are broadly classified into two groups based on the type of transducer and bioreceptor
type. Fig. 1.1 shows the different classes of biosensors.
10 Tools, techniques and protocols for monitoring environmental contaminants

Fig. 1.1 Classification of biosensors.

3.1 Aptasensors for detection of emerging contaminants

Aptamers are the single-stranded DNA or RNA of known sequences, have high affinity
and specificity to the target molecules to be detected. Aptamer-based technologies have
gained tremendous interest in sensing a potentially large number of environmental con-
tamination in recent time due to their higher sensitivity, selectivity, less expensive in vitro
system, and enhanced environmental stability. An aptasensor consists of known oligonu-
cleotide sequence, that is, aptamer as the sensing element either combined within the
system or closely associated with a physiochemical transducer system [61]. Beside the sig-
nificant application of aptasensor in medical field, this technique is now more popular as
the sensor system of several environmental contaminants including heavy metals, toxins,
pesticides, and other harmful small molecules. Mycotoxins, the major group of toxins
that are present in our food have been detected by this aptasensor [62]. Recently, a num-
ber of heavy metals including As3+, Cu2+, and Pb2+ have been detected from contam-
inated water sample at very low concentration by this technique [63]. A series of aptamers
which bind to with high affinity to different poisonous organo-phosphorous pesticides
such as phorate, profenofos, isocarbophos, and omethoateas has already been developed
[64]. Aptasensors capable of rapidly detecting pathogens including both virus and bacteria
with improved analytical performance have been designed without prior information of
their molecular structures [65]. In the environmental monitoring, the application of elec-
trochemical aptasensors is immense, and this is one of the fascinating areas. The future
progress in aptasensors technology will reveal the detection of unexplored target analytes
relevant to the environmental contaminants.
 An overview of analytical methodologies for environmental monitoring 11

3.2 Enzyme and whole cell biosensors

Enzyme biosensor employed various groups of enzymes such as laccase, tyrosinase, per-
oxidases, acetyl cholinesterase, cytochrome P450, monoamine oxidase as recognition
element [65–68]. They have wide applications in monitoring environmental contami-
nants including phenols and their degradative products [65, 66], pesticides [69], herbi-
cides [70], and pharmaceuticals [67]. A couple of portable enzyme-based biosensors
have also been reported in literature for on-site pesticide detection [71, 72].
The main advantages of using enzyme-based biosensors include short analysis time
(analysis sample within minutes or hours) and no ethical issues associated with them.
However, they are costlier and can detect narrower range of pollutants than whole cell
biosensors. Enzyme biosensors detect a group of pollutants, for example, total pesticides
rather than individual pollutant. On the other hand, whole cell (bacteria, yeast, algae)
based biosensors are inexpensive and easy but have ethical issues. The analysis time of
whole cell-based biosensors is in hours to days [59].
Yeast biosensors (an example of whole cell biosensors) have been developed for selected
endocrine disruptors (EDC) such as estrogens [73], glucocorticoids [74], bisphenol A [75],
serotonin [76], and so on, and selected heavy metals [77, 78]. Therefore yeast biosensor for
other ECs needs to be developed for its wider and real world applications. Long-term stor-
age of yeast biosensors is challenging and needs further advancements. Few authors sug-
gested and tested the storage of yeast biosensors at low temperature ( 18 or 20°C) to
maintain the viability of cells for up to 10–12 months [79, 80]. However, reactivation
of yeast cells from deep freeze storage before on-site analysis may need several hours [59].

3.3 Immunosensors
Immunosensors are based on the immunochemical techniques such as ELISA to detect
the ECs in the environment. They utilize the antibody or antigen as bioreceptor to pro-
duce signals and a transducer (electrochemical, optical, piezoelectric, etc.) to convert the
biosignals into readable form. Immunosensors are highly selective and can be used to
study the toxicity of an individual pollutant [81]. Mauriz et al. [82] had continuously
monitored the chlorpyrifos, an organophosphate pesticide at part per trillion levels in real
water samples (groundwater, surface water, and drinking water) using a portable immu-
nosensor. The portable immunosensor took only 20 min for the analysis without sample
preparation such as extraction or cleanup.

3.4 Molecularly imprinted polymer (MIP) biosensors

MIP-based sensors have been gaining huge attention in recent times. The basic working
principle of MIP is the creation of highly stable ligand with specific and selective craters in a
3D-polymeric network, complementary to the target analytics by polymerization of a
monomer and a cross-linker. The cavity not only is complementary with respect to target
12 Tools, techniques and protocols for monitoring environmental contaminants

molecule’s shape, size, and conformation but also provides covalent and noncovalent inter-
action points and a coordination sphere for proper conjugation of the template molecule
[83]. MIPs are synthetic polymers, which can only be used as affinity sensors but not as a
catalytic biochemical enzyme mimicking sensors [84]. This technology has been described
as promising analytical devices in diverse fields, including environmental, food, pharma-
ceutical, and clinical analysis [84]. MIP technology is advantageous with respect to its
desired portability, quick response, high specificity, acute sensitivity, and less price. For
effective detection, MIP-based sensors should be coupled with various transducers systems
including electrochemical, optical, conductometric, fluorescence, and piezoelectric [85].
MIPs are along with other analytical techniques such as LC, capillary electrochromatogra-
phy, SPE, binding assays, and so on, also used as selective tools for the detection of various
inorganic and organic environmental pollutants [86].
The applications of MIP biosensors have already been in success in analyzing volatile
organics from their mixtures, studying degradation of hydrocarbon, detecting pesticides,
pharmaceutical compounds in polluted environmental sample, in evaluating oxidation-
reduction reactions, in bio-analyzing of signaling molecules/drugs by targeting whole cells,
viruses, or bacteria [87–91]. A combination of MIPs and transducers form a synergistic
device. MIPs should have fulfilled certain criteria during fabrication. They should have
proper selectivity, binding strength, regeneration ability and stability in terms of withstand-
ing extreme pH, organic base, high temperature and pressure during operational condition
as well as during storage [87, 92]. Moreover, this technology is quite suitable and advan-
tageous for the detection of nonelectroactive molecules such as pesticides, drugs, and so on.
Despite the plentiful advantages of MIPs the rate of commercial activity is still limited.

3.5 Nanomaterial-based biosensors

Nanomaterial-based biosensors are also attracting a lot of attention due to its unique char-
acteristics and advantages over other biosensors. Nanomaterials offer a very high surface
area-to-volume ratio, which enhances the catalytic function and sensing response [93].
They also offer great biochemical compatibility with very low detectable limits. Silver
nanoparticle-based electrochemical biosensors have been developed for the detection
and monitoring of estrogenic substances in water samples with detection limits of up
to 1 ng/L [94]. Recently, Pd wormlike nanochains/graphitic carbon nitride nanocom-
posites and acetylcholinesterase-based biosensors were developed for the detection of
organophosphate pesticides with good reproducibility and stability [95]. Hassaan et al.
[96] developed optical nano-biosensors for the detection of pharmaceuticals and other
contaminants. The authors used horseradish peroxidase enzyme as a bioreceptor for
the detection and quantification of phenol, resorcinol, epinephrine, and acetaminophen.
However, application of such optical nano-biosensors for real environmental matrices
needs to be verified.
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