Review

Electrochemical and Colorimetric Nanosensors for Detection of

Heavy Metal Ions: A Review
Sayo O. Fakayode 1,*, Charuksha Walgama 2, Vivian E. Fernand Narcisse 3 and Cidya Grant 3

1 Department of Chemistry, Physics and Astronomy, Georgia College and State University,
Milledgeville, GA 31061, USA
2 Department of Physical and Applied Sciences, University of Houston-Clear Lake, Houston, TX 77058, USA;

[email protected]
3 Department of Chemistry, Forensic Science and Oceanography, Palm Beach Atlantic University,

West Palm Beach, FL 33401, USA; [email protected] (V.E.F.N.); [email protected] (C.G.)

* Correspondence: [email protected]

Abstract: Human exposure to acute and chronic levels of heavy metal ions are linked with various
health issues, including reduced children’s intelligence quotients, developmental challenges,
cancers, hypertension, immune system compromises, cytotoxicity, oxidative cellular damage, and
neurological disorders, among other health challenges. The potential environmental HMI
contaminations, the biomagnification of heavy metal ions along food chains, and the associated risk
factors of heavy metal ions on public health safety are a global concern of top priority. Hence,
developing low-cost analytical protocols capable of rapid, selective, sensitive, and accurate
detection of heavy metal ions in environmental samples and consumable products is of global public
health interest. Conventional flame atomic absorption spectroscopy, graphite furnace atomic
absorption spectroscopy, atomic emission spectroscopy, inductively coupled plasma–optical
emission spectroscopy, inductively coupled plasma–mass spectroscopy, X-ray diffractometry, and
X-ray fluorescence have been well-developed for HMIs and trace element analysis with excellent
but varying degrees of sensitivity, selectivity, and accuracy. In addition to high instrumental
running and maintenance costs and specialized personnel training, these instruments are not
Citation: Fakayode, S.O.; portable, limiting their practicality for on-demand, in situ, field study, or point-of-need HMI
Walgama, C.; Fernand Narcisse, V.E.; detection. Increases in the use of electrochemical and colorimetric techniques for heavy metal ion
Grant, C. Electrochemical and detections arise because of portable instrumentation, high sensitivity and selectivity, cost-
Colorimetric Nanosensors for effectiveness, small size requirements, rapidity, and visual detection of colorimetric nanosensors
Detection of Heavy Metal Ions: A that facilitate on-demand, in situ, and field heavy metal ion detections. This review highlights the
Review. Sensors 2023, 23, 9080.
new approach to low-cost, rapid, selective, sensitive, and accurate detection of heavy metal ions in
https://doi.org/10.3390/s23229080
ecosystems (soil, water, air) and consumable products. Specifically, the review highlights low-cost,
Academic Editors: Angeliki portable, and recent advances in smartphone-operated screen-printed electrodes (SPEs), plastic chip
Brouzgou and Carmelo Lo Vecchio SPES, and carbon fiber paper-based nanosensors for environmental heavy metal ion detection. In
Received: 22 October 2023
addition, the review highlights recent advances in colorimetric nanosensors for heavy metal ion
Revised: 5 November 2023 detection requirements. The review provides the advantages of electrochemical and optical
Accepted: 7 November 2023 nanosensors over the conventional methods of HMI analyses. The review further provides in-depth
Published: 9 November 2023 coverage of the detection of arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), mercury (Hg),
manganese (Mn), nickel (Ni), lead (Pb), and zinc (Zn) ions in the ecosystem, with emphasis on
environmental and biological samples. In addition, the review discusses the advantages and
Copyright: © 2023 by the authors. challenges of the current electrochemical and colorimetric nanosensors protocol for heavy metal ion
Licensee MDPI, Basel, Switzerland. detection. It provides insight into the future directions in the use of the electrochemical and
This article is an open access article colorimetric nanosensors protocol for heavy metal ion detection.
distributed under the terms and
conditions of the Creative Commons Keywords: heavy metal ion detections; portable electrochemical nanosensors; colorimetric
Attribution (CC BY) license nanosensors; review
(https://creativecommons.org/license
s/by/4.0/).

Sensors 2023, 23, 9080. https://doi.org/10.3390/s23229080 www.mdpi.com/journal/sensors

Sensors 2023, 23, 9080 2 of 27

1. Introduction and Overview

The industrial revolution and radical technological advancement in the past decades
increased the global population, urbanization, manufacturing and transportation of
consumable goods, and access to health care. Technological advancement has also
facilitated and improved standards of living, quality of human life, and life expectancy.
Nonetheless, demand for the industrial revolution, technological advancement, and
global population growth has come at a severe cost with unintended negative impacts on
ecosystems and natural resources. For instance, unintended consequences of
anthropogenic activity and industrial development have generated and liberated tons of
environmental waste materials and toxic chemicals of concern, including toxic heavy
metal ions, into the ecosystem (soil, water, and air). The influx of untreated industrial
effluent, municipal wastes, agricultural and urban runoff into surface rivers, landfilled
metal and electronic waste, automobiles, and mechanic shops continue to pose significant
challenges in terms of environmental heavy metal ion contamination and ecological
degradation. The aging of infrastructure, corrosion, the degradation of municipal water
and sewage distribution piping systems, coal burning, construction, oil and mining,
metallurgy, smelters, leather tanning, electroplating, inorganic dyes, batteries,
petrochemicals, paints, agrochemicals, and the chemical fertilizers industry constitute
primary sources of environmental heavy metal ion contamination [1–8]. Ecosystems,
including humans, are exposed to heavy metal ion contaminations through direct point
and non-pollution sources, occupational exposure, dietary intake of heavy metal-
contaminated water or polluted food items, or inhalation of heavy metal from air
particulates.
Ecological and public health risk factors from the exposure to heavy metals is
concerning because of the long residence time of heavy metals in the environment.
Chronic and acute concentrations and heavy metal accumulation have been well
documented and widely reported in soil and sediment, surface water, underground
water, plants, food crops, fish, seafood, aquatic animals, and terrestrial animals [9–37].
Heavy metals are susceptible to bioaccumulation and biomagnification in plants, animals,
and human organs via the food chain and trophic levels. Studies have also reported acute
to chronic heavy metal ion toxic effects in human organs [10–36]. The exposure of animals
and plants to heavy metal contamination and the resulting health risk factors, including
oxidative stress, ecotoxicities, phytotoxicity, and physicochemical and biochemical
changes on animals and plants, are concerning [38–43]. In addition, various health
hazards, including reduced children’s intelligence quotients, developmental challenges,
cancers, elevated blood pressure, immune system compromises, cytotoxicity, oxidative
cellular damage, cardiovascular diseases, myocardial infarction, neurological disorders,
and miscarriages and stillbirths, among other health challenges, have also been linked to
elevated levels of heavy metals in humans [44–62]. The recent lead tap water crisis in Flint,
Michigan, and the resulting health risk factors and social and post-traumatic stress
disorders are a wake-up call for being ready for potentially widespread heavy metal
contaminations [63–70]. Developing effective environmental heavy metal ion detections is
paramount to ensuring public health safety and global homeland security.

Conventional Heavy Metal Ion Analysis and Trace Element Detection Methods
Notable progress has been made in developing capable analytical protocols for
detecting, analyzing, and screening heavy metal ions in environmental samples (Figure
1). For instance, conventional flame atomic absorption spectroscopy (FAAS), graphite
furnace atomic absorption spectroscopy (GF-AAS), atomic emission spectroscopy (AES),
inductively coupled plasma–optical emission spectroscopy (ICP-OES), inductively
coupled plasma–mass spectroscopy (ICP-MS), X-ray diffractometry, and X-ray
fluorescence [71–84] have been well-developed for heavy metal and trace elements.
Nonetheless, some techniques have significant drawbacks and challenges that limit their
Sensors 2023, 23, 9080 3 of 27

practical applications. For example, FAAS requires a large sample size, flammable fuels,
and a relatively expensive cathode lamp for each element (though a multi-element
cathode lamp is available, it suffers from element interference). Background, spectra, and
chemical ionization interferences are problematic in FAAS. The oxidation of carbon
graphite in GF-AAS constitutes a challenge in GF-AAS. ICP-OES and ICP-MS instruments
require ultra-pure argon gas. X-ray diffractometry is expensive and less sensitive for metal
ion analysis at ultra-trace levels.
In addition to high instrumental running and maintenance costs and specialized
personnel training, these instruments are not portable, limiting their practicality for on-
demand, in situ, field study, or point-of-need heavy metal ion detection. Electrochemical
and colorimetric nanosensors are viable alternative strategies that address some of the
challenges of the available HMI detection methods. Toward this effort, various
electrochemical nanosensors have generated significant interest in detecting heavy metal
ions in recent years [85]. Increases in the use of electrochemical techniques for heavy metal
ion detections arise because of high sensitivity and selectivity, cost-effectiveness, a small
size requirement, and the rapidity of electrochemical methods. For instance,
electrochemical sensors also have portable instrumentation and are sometimes
disposable, facilitating on-demand, in situ, and field heavy metal ion detections. Hu et al.
2023 have comprehensively reviewed the advances and advantages of portable heavy
metal analysis sensors [85].

Figure 1. Conventional instrumental methods of heavy metal ion and trace element analysis in
environmental samples.

In addition, electrochemical sensors and colorimetric nanosensors have been

developed, allowing rapid screening and visual detection for point-of-use, in situ, and
field heavy metal ion detections. In a review article, Ullah et al. 2018 recently emphasized
innovation and advancements of nanomaterial-based optical sensors for heavy metal
analysis [86]. This review highlights the new approach to low-cost electrochemical and
colorimetric nanosensors for fast, selective, sensitive, and accurate detection of HMIs in
ecosystems (soil, water, and air) and biological samples. Specifically, this review
highlights low-cost portable electrochemical nanosensors and recent advances in
smartphone-operated screen-printed electrodes (SPEs), plastic chip SPES, and carbon
fiber paper-based and microfluidic-based nanosensors for selective environmental heavy
metal ion detection. This review also provides up-to-date advances in optical sensors for
the fast detection and analysis of heavy metal ions. In addition, this review provides in-
depth coverage of the detection of Arsenic(III) and Arsenic(IV), Cr(III) and Cr(IV), Hg(I)
and Hg(II), Pb(II) and Pb(IV), Manganese (II), Fe(II), and Fe(III) ions in environmental and
Sensors 2023, 23, 9080 4 of 27

biological samples and consumable products. Moreover, the review discusses the
advantages and shortcomings of the current electrochemical and colorimetric nanosensors
protocol for heavy metal ion detection and future directions for heavy metal ion detection.

2. Portable Electrochemical Nanosensors for the Detection of Heavy Metal Ions in

Environmental Samples
Heavy metal pollution is a significant environmental concern due to its potential to
harm ecosystems, human health, and aquatic life. Heavy metals become pollutants when
they enter water bodies at elevated concentrations, often due to industrial processes,
urban runoff, and anthropogenic activities. Some common heavy metals of concern in
wastewater include lead, mercury, cadmium, chromium, arsenic, and nickel. Continuous
water quality monitoring and research into the sources and effects of heavy metal
pollution are essential for developing effective mitigation strategies. Among various
analytical techniques, electrochemical detection is a powerful and widely used method
for quantifying and monitoring heavy metals in different environmental samples,
including water, soil, and air [87,88]. In this regard, portable and disposable
electrochemical sensors have generated considerable attention because of their ease of use,
cost-effectiveness, and suitability for on-site monitoring [89–93]. These sensors are
designed to be user-friendly, providing rapid and reliable measurements without the
need for extensive sample preparation or sophisticated equipment. Their sensitivity and
selectivity towards heavy metal pollutants are critical in method development.
Nanomaterials play a fundamental and crucial role in the fabrication process of
electrochemical sensors. Nanomaterials offer stable support structures and highly active
sites for functionalization, making them excellent candidates for improving the selectivity
and sensitivity of electrodes in heavy metal detection [92].
In recent years, there has been a growing interest in leveraging nanomaterials to
enhance the effectiveness of electrode surfaces in detecting heavy metals. Modified
electrodes incorporating nanomaterials have proven decisive in electroanalytical methods
for identifying a wide range of heavy metals. Such nanomaterials include metal
nanoparticles, metal oxides, graphene-based materials, carbon nanotubes, and metal–
organic frameworks (MOFs). Standard nanomaterial fabrication techniques on disposable
electrodes include drop casting, dip coating, spin coating, electrochemical deposition,
direct growth, and screen printing [93]. Table 1 summarizes the latest studies that have
employed various nanostructure architectures in conjunction with screen-printed
electrodes (SPE) for the portable detection of heavy metal pollutants in environmental
samples.
Huang and coworkers [94] have demonstrated that phosphorus-doped biochar–
attapulgite/bismuth film electrodes decorated with magnetic Fe3O4 nanoparticles (MBA-
BiFE) can be utilized to detect Cd(II), Pb(II), and Hg(II) with limits of detection of 0.036
nM, 0.003 nM, and 0.011 nM, respectively. They showed that a machine learning model
based on an artificial neural network (ANN) can perform multi-metal analysis using the
data generated from a portable wireless smart sensor, connected to the modified screen-
printed electrode [94]. Similarly, core-shell Fe3O4@Au nanoparticles anchored with
cysteamine have been used to prepare a composite with thymine acetic acid
(Fe3O4@Au/CA/T-COOH) for Hg(II) detection in the range of 1–200 µg/L in wastewater
samples [95]. Moreover, silver nanowires and butterfly-shaped silver nanoparticles have
been successfully employed to detect Cd(II), Pb(II), Cu(II), and Hg(II) in ppb levels using
disposable SPEs [96,97]. Among carbonaceous nanomaterials, carbon nanotubes and
graphene are widely employed to modify screen-printed electrodes. Hajzus et al. [98]
investigated a sensitive platform for the selective voltammetric measurement of CdCl2,
CuSO4, HgCl2, and PbCl2 in seawater based on epitaxial graphene-modified SiC paper.
They implemented machine learning models to accurately identify heavy metal types
based on cyclic square wave voltammograms. In another study, Bao et al. [99] constructed
an SPE modified with chitosan/PANi–Binanoparticle@graphene oxide multi-walled
Sensors 2023, 23, 9080 5 of 27

carbon nanotubes (CS/PANi–Bi NP@GO–MWCNT) for the rapid detection of Cu(II) and
Hg(II) ions. Their portable detection platform comprises an in situ signal analysis circuit,
a Bluetooth chip, a photocured 3D-printed shell, and an electrode sleeve interface. This
portable electrochemical sensor was tested for Hg (II) and Cu (II) with detection limits of
10 ppb and 0.998 ppm, respectively, as given in Table 1.
Metal–organic frameworks (MOFs) are a novel category of nanoporous materials that
demonstrate efficacy as a highly effective platform for the electrochemical sensing of
heavy metals. MOFs can be designed with specific pore sizes and functional groups
tailored to capture and bind to heavy metal ions selectively. Tan et al. [100] developed a
novel hybrid material featuring a hetero-shelled hollow structure composed of metal–
organic framework (MOF) components, denoted as HCZ@UN. This involved utilizing
hollow carbonized ZIF-8 (HCZ) as a substrate for the growth of UiO-66(Zr)–NH2 (UN) on
an SPE for the efficient detection of Pb (II) ions in tap water samples in the range of 0.100–
500 nM. Qi and coworkers designed an electrochemical sensor for Cd (II) detection using
a complex of carbon fiber paper (CFP), CoMOF, AuNPs, and glutathione as the conductive
substrate (CFP/CoMOF/AuNPs/GSH). They achieved Cd (II) detection as low as 1 nM
[101]. In a related study, Wang et al. employed a covalent organic framework prepared
with the condensation of 2,5-diamino-1,4-phenyldicarboxylic acid (DATA), and 2,4,6-
triformylphloroglucinol (TP). Here, the uniformly distributed -COOH and NH groups on
the pore’s wall were utilized as heavy metal ion adsorption sites. The electrochemical
sensor could detect Hg(II), Cu(II), Pb(II), and Cd(II) simultaneously, and the limit of
detection was at sub-nanomolar levels [102] (See Table 1).
In addition to the nanostructures mentioned above, various other materials are also
utilized to modify SPEs. These materials include chemically functionalized isoporous
[103] and mesoporous [104] silicon membranes, ion-imprinted polymer films [105], and
electrodeposited bismuth films [106,107]. These modifications have been employed for the
sensitive and selective detection of several heavy metal ions such as Cd(II), Pb(II), Cu(II),
Hg(II), Zn(II), and As(III) in environmental samples, as detailed in Table 1.

2.1. Portable Electrochemical Nanosensors for the Detection of Heavy Metal Ions in
Biological Samples
Diagnosis of heavy metals in humans typically involves blood or urine laboratory
tests to measure the concentrations of heavy metals in the body using inductively coupled
plasma–mass spectrometry (ICP-MS). Table 2 indicates the reference levels based on the
CDC guidelines and heavy metal screening blood and urine test catalogs of Mayo Clinic
Laboratories.

Table 1. Summary of recent reports on the detection of heavy metals in environmental samples
using nanostructure-modified electrodes.

Electrochemical
Metal
Electrode Modification Detection Portability Linearity LOD Sample Ref.
Ions
Method
Phosphorus-doped biochar–
attapulgite/bismuth film Cd(II) 0.1 nM–5 µM, 0.036 nM
Smartphone- Tap water
electrode decorated with SWASV Pb(II) 0.01 nM–7 µM, 0.003 nM [94]
operated SPE Lake water
magnetic Fe3O4 Hg(II) 0.1 nM–3 µM 0.011 nM
nanoparticles (MBA-BiFE)
Thymine acetic acid anchored
with cysteamine-conjugated
SPE/plastic chip 1–200 µg/L and
core-shell Fe3O4@Au DPASV Hg(II) 0.5 µg/ L Wastewater [95]
sample holder 200–2200 µg/L
nanoparticles (Fe3O4@Au/
CA/T-COOH)
Butterfly-shaped silver Cd(II) 5–300 ppb 0.4 ppb Tap water
DPASV SPE [96]
nanostructure (AgNS) Pb(II) 5–300 ppb 2.5 ppb Rainwater
Sensors 2023, 23, 9080 6 of 27

Cu(II) 50–500 ppb 7.3 ppb Lake water

Hg(II) 5–100 ppb 0.7 ppb
Silver nanowires,
hydroxymethyl propyl cellulose, Drinking
CV SPE Hg(II) 5–25 µM 3.94 µM [97]
chitosan, and urease water
(AgNWs/HPMC/CS/Urease)
CdCl2
Portable in-
CuSO4 Spiked samples
Epitaxial Graphene on SiC CSWASV house built - Sea water [98]
HgCl2 100–3000 ppb
potentiostat
PbCl2
Portable device
with an in situ
Chitosan/PANi–Bi signal analysis
nanoparticle@graphene oxide circuit, a
Hg(II) 10 ppb
multi-walled carbon nanotubes DPV Bluetooth chip, a Tap water [99]
Cu(II) 0.998 ppm
(CS/PANi–Bi NP@GO– photocured 3D-
MWCNT) printed shell,
and an electrode
sleeve interface
Zirconium-based MOF material, 0.0492 ±
DPASV SPE Pb(II) 0.100–500 nM Tap water [100]
UiO-66(Zr)–NH2 0.00523 nM
Carbon fiber paper, CoMOF,
Carbon fiber Lake water
AuNPs, and glutathione SWV Cd(II) 0.001–1 µm 1.0 nM [101]
paper electrode River water
(CFP/CoMOF/AuNPs/GSH)
Hg(II) 0.0085–8.00 µM 2.80 nM
Covalent organic framework Cu(II) 0.015–8.00 µM 5.01 nM
SWASV SPE River water [102]
(COFDATA-TP) Pb(II) 0.0056–8.00 µM 1.83 nM
Cd(II) 0.0069–8.00 µM 2.91 nM
Cd(II) 0.2–20.0 µM 9.3 nM
Silica isoporous membrane Pb(II) 0.01–10.0 µM 1.1 nM
SWASV SPE Soil [103]
(SIM) Cu(II) 0.2–20.0 µM 16.2 nM
Hg(II) 0.01–10.0 µM 1.4 nM
SBA-15
Chemically decorated Cd(II) 5–80 µg/L 0.22 µg/L
mesoporous silica (SBA-15 and Pb(II) 10–80 µg/L 0.36 µg/L Tap water
SWV - [104]
MCM-41) with L-cysteine (L- MCM-41 5–80 µg/L 0.23 µg/L Lake water
cys). Cd(II) 10–80 µg/L 0.76 µg/L
Pb(II)
Drinking
water
Ion-imprinted polymer film (IIP) CV SPE Cd(II) 10–1200 nM 1.71 nM Tap water [105]
Marine
water
Screen–printed gold working Pb(II) 0.04 µg/L
Industrial
electrode with electroplated SWASV SPE Cd(II) 10–120 µg/L 0.02 µg/L [106]
wastewater
bismuth film (Bi/SPAuE) Zn(II) 0.23 µg/L
Tap water
Cd(II) 0.03 µg/ L Mountain
Hg/Bi-plated glassy carbon SWASV
- Pb(II) - 0.05 µg/ L spring [107]
electrode LSASV
As(III) 0.15 µg/ L water
River water
DPASV—differential pulse anodic stripping voltammetry; SWASV—square wave anodic stripping
voltammetry; CV—cyclic voltammetry; SWASV—square wave anodic stripping voltammetry;
SWV—square wave voltammetry; DPV—differential pulse voltammetry; LSASV—linear sweep
anodic stripping voltammetry.
Sensors 2023, 23, 9080 7 of 27

Table 2. Reference range of heavy metals in human biofluids.

Normal Values *
Metal
Blood Urine
0–17 years: Not established
As <13 ng/mL (all ages)
> or = 18 years: < 24 g/g creatinine
0–5 years: < 3.5 g/dL
> or =6 years: < 5.0 g/dL
0–17 years: Not established
Pb Critical values
> or = 18 years: < 0.6 g/g creatinine
Pediatrics (< or =15 years): > or = 20.0 g/dL
Adults (> or = 16 years): > or = 70.0 g/dL
0–17 years: Not established
Cd <5.0 ng/mL (all ages)
> or = 18 years: < 2 g/g creatinine
0–17 years: Not established
Hg <10 ng/mL (all ages)
> or = 18 years: < 2 g/g creatinine
* Reference levels are reported based on the CDC guidelines and Heavy Metals Screen with
Demographics, Blood (HMDB) test and the Heavy Metal/Creatinine Ratio with Reflex, Random,
Urine (HMUCR) test provided by Mayo Clinic Laboratories as of 09/2023 [108,109].

Given that blood is an intricately complex biological fluid, there have been recent
advancements in the development of portable electrochemical sensor platforms designed
for the non-invasive detection of heavy metals in bodily fluids such as urine, saliva, and
sweat [110–112]. This review section focuses on recent developments in portable
electrochemical devices capable of detecting heavy metals within clinically relevant
concentration ranges.
Ma and their research team have designed a microfluidic electrochemical sensing
chip that relies on a smartphone-based electrochemical workstation to detect Pb2+ in
human serum (see Figure 2) [112]. To enhance the surface area and conductivity, they have
harnessed a nanocomposite of silver nanoparticles, reduced graphene oxide, and nickel
hydroxide on a nickel form (Ag-rGO-f-Ni(OH)2/NF) as the working electrode.
Furthermore, they have shown that incorporating a thermocapillary convection process
within the microfluidic platform promotes electrolyte flow and expedites electron
transfer, reducing assay times and amplifying electrochemical signals. This innovative
device could generate differential pulse voltammetry (DPV) signals for Pb(II) within the
0.01–2100 µg/L concentration range.
Similarly, Wang and colleagues have introduced a microfluidic paper-based
analytical device (µPAD) capable of isolating proteins and detecting lead ions in urine
samples. [113]. Proteins are well-known for fouling electrodes, posing a challenge for the
direct electrochemical detection of heavy metals in urine. To address this issue, the
authors have modified the sample zone of the paper device with (NH4)2SO4 to precipitate
urinary proteins through a salting-out effect upstream of the detection zone. This portable
paper sensor exhibits a linear range of 10–500 µg/L with a detection limit of 9 µg/L for
detecting Pb(II) in urine, utilizing anodic stripping voltammetry (ASV).
Magnetic sorbents offer a unique combination of impressive sorption capacity while
being conveniently manipulated by an external magnetic field, eliminating the need for
labor-intensive filtration or centrifugation processes during phase separation. This dual
advantage reduces the overall operation time and enhances the portability and feasibility
of on-site extractions, making the procedure more accessible and efficient. In a distinct
study, Fernández and their team employed magnetic dispersive solid-phase extraction
(MDSPE) in conjunction with electrochemical detection, utilizing a screen-printed carbon
electrode to determine the presence of Pb(II). In addition to lead, similar electrochemical
approaches have been successfully integrated into microfluidic portable platforms for the
detection of cadmium [114–116], mercury [117], and zinc [118].
Sensors 2023, 23, 9080 8 of 27

Figure 2. (A) The preparation of 3D Ag-rGO-f-Ni(OH)2/NF composites, (B) The manufacturing

process of the microfluidic device, (C) The 3D Ag-rGO-f-Ni(OH)2/NF microfluidic sensor for
electrochemical sensing Pb2+ Reproduced from Ref. [112] with permission from Elsevier.
Sensors 2023, 23, 9080 9 of 27

2.2. Portable Electrochemical Nanosensors for the Detection of Heavy Metal Ions in
Food Samples
Heavy metal food contamination is a significant and concerning issue with far-
reaching implications for public health, agriculture, and the environment [119,120].
Unfortunately, due to escalating environmental and industrial pollution levels, heavy
metals have become pervasive in everyday food items, including vegetables, fruits, meat,
marine food, and water sources. Therefore, it is essential to institute measures to detect
and continually monitor heavy metal levels in our food supply. In this context, this section
presents a summary of the most recent articles published on the detection of heavy metals
in food. As discussed in the previous sections, using paper-based SPEs with
nanostructure modifications on the transducer surface enhances the portability and
sensitivity of the electrochemical detection platform [121,122]. Furthermore, a distinct
sample preparation method must be employed when dealing with actual food samples to
extract heavy metals into an acidic matrix after digestion or an ashing process.
Recently, Pang et al. [123] developed a stack-up electrochemical device modified
with an amino-functionalized cobalt-based metal–organic framework and gold
nanoparticles (Co-MOF-NH2/AuNPs/CPE) to detect heavy metals in various food
samples. Their method enabled the simultaneous detection of Pb(II) and Cd(II) with
detection limits of 7.0 × 10–2 and 1.1 × 10–2 ng/mL, respectively, in natural food samples
such as drinking water, juice, tea, grains, fruits, vegetables, liver, and aquatic products. In
the sample preparation process, solid samples were initially crushed using a tissue
shredder and then digested using concentrated nitric acid and a 30% hydrogen peroxide
solution. Subsequently, the extracts were decomposed using a microwave and heated on
a graphite digestion apparatus until they were mixed with an acetate buffer (pH 5.0) for
the final analysis [123] (See Figure 3).
Pungjunun and colleagues have introduced a sensor design featuring a bismuth
nanoparticle-modified screen-printed graphene electrode (BiNP/SPGE) integrated into a
paper-based analytical device. This setup allows for the simultaneous determination of
Sn(II) and Pb(II) while incorporating a portable potentiostat for enhanced mobility and
convenience. Under optimal conditions, the linear range for both metals spans from 10 to
250 ng/mL, with a calculated limit of detection values of 0.26 and 0.44 ng/mL for Sn(II)
and Pb(II), respectively. This device has been utilized to analyze the above heavy metal
ions in canned food samples (mushrooms and bamboo shoots). Solid samples were
ground into a fine powder using a blender and digested with a 2% v/v HNO3 solution.
Then, the pH was adjusted to pH 7 using NaOH solution and diluted with oxalic acid and
cetyltrimethylammonium bromide (CTAB) for electrochemical analysis.
Sensors 2023, 23, 9080 10 of 27

Figure 3. (A) The preparation of Co-MOF-NH2/AuNPs/CPE and (B) analytical procedure on stack-
up electrochemical device. Reproduced from Ref. [123] with permission from Elsevier.

Rice is a staple food globally, especially in Asia, Africa, and the Middle East. Rice is
prone to take up and bioaccumulate heavy metals, especially Pb, Cd, As, and Hg, from
contaminated soil or irrigated agricultural water. The intake of heavy metal contaminated
rice can pose health risks to consumers, as these heavy metals are toxic with negative
health implications, including organ damage and cancer. Jiang et al. recently developed a
smartphone-based electrochemical cell to evaluate the toxicity of Cd(II), Pb(II), and Hg(II)
ions on Hep G2 cells as an indirect measurement of heavy metals in the analyte sample
[124]. Here, the sensor was fabricated with reduced graphene oxide (RGO)/molybdenum
sulfide (MoS2) composites to significantly improve the biological adaptability for
immobilizing Hep G2 cells. Differential pulse voltammetry (DPV) was employed to
measure the electrical signals induced by the toxicity of heavy metal ions. The IC50 values
for Cd(II), Pb (II), and Hg (II) were calculated as 49.83 µM, 36.94 µM, and 733.90 µM,
respectively, by the electrochemical method. They utilized those cytotoxicity curves (the
curve between heavy metal concentration and cell inhibition rate) to quantify levels of
heavy metals in spiked rice samples after a wet digestion process. In another study, a
glassy carbon electrode modified with silver nanoparticles (AgNP), bismuth nanoparticles
(BiNP), multiwalled carbon nanotubes (MWCNT), and Nafion was utilized to detect
Cd(II) and Pb(II) with the LODs of 25.12 ppb and 20.55 ppb, respectively. The rice samples
were analyzed after an ashing and acid digestion process [125].
Voltammetry, impedimetry, potentiometry, conductometry, and amperometry
represent the primary techniques employed in the electrochemical detection of heavy
metals in all the studies mentioned above [126]. Various methodologies are utilized within
the realm of voltammetry, including cyclic voltammetry, linear sweep voltammetry,
differential pulse voltammetry, and square wave voltammetry. Additionally, stripping
voltammetry comprises three fundamental variants: anodic stripping voltammetry (ASV),
cathodic stripping voltammetry (CSV), and adsorptive stripping voltammetry (AdSV).
The essence of stripping analysis lies in a two-step process: an initial pre-concentration
step on the working electrode (reduction), followed by a subsequent step that removes the
accumulated heavy metal ions from the electrode’s surface (oxidation) through a Faradaic
Sensors 2023, 23, 9080 11 of 27

reaction, thereby returning the heavy metal ions into the solution. This final process
generates a current signal proportional to the solution’s heavy metal concentration.

3. Colorimetric (UV‐Visible) Nanosensors for Heavy Metal Ion Detections

Colorimetric nanosensors can be categorized, according to their route/manner of
synthesis, into (1) green synthesis nanomaterials and (2) chemical or biological synthesis
nanomaterials [127]. The overall principle of colorimetric nanosensors is based on the
binding and affinity interaction between nanosensors and metal ions, causing a change in
absorbance (Figure 4). The development of colorimetric nanosensors is strongly associated
with the type of fabrication material. The mode of action for colorimetric detection can be
attributed to (1) localized surface plasmon resonance (LSPR) phenomenon and (2)
nanozyme or nanozyme-like properties of the material. LSPR-based colorimetric sensors
are usually fabricated from metal nanoparticles (e.g., gold, silver) since they each have a
specific absorbance band, giving them a selective response to heavy metals. The principle
of LSPR-based colorimetric sensors relates to a color change of the metal nanoparticle via
an aggregation or etching process, stemming from the characteristic absorption band. For
the synthesis of nanozyme-assisted colorimetric sensors, nanoscale materials with
catalytic properties are used that can detect low concentrations of heavy metal ions. The
catalytic activity of these nanozymes can be stimulated or inhibited when metal ions
interact or absorb on the nanozyme surface [128,129]. During these chemical reactions, a
color change is produced. Table 3 summarizes the various types of colorimetric sensors
reviewed in this section.

Figure 4. Scheme of colorimetric-based nanosensors for the detection of heavy metals.

Sensors 2023, 23, 9080 12 of 27

Table 3. Recent advances in colorimetric (UV-Vis) nanosensors for heavy metal ion detection.

Observed/Detected
Heavy
Color Change Sample Type
Metal Nanosensor Material LOD Linear Range Ref.
(Absorbance Examined
Target
Wavelength of Interest)
Environmental Samples
Thiazolylazopyrimidine
-functionalized TiO2 Yellow to red
Cu2+ Water 2.51 nM 0.01–12.5 µM [130]
nanosensor (A536)
(TiO2-TAP)
Deep yellow to purple
Cr3+ Multi-functional iodide-
(A390/A520) for Cr3+; Environmental 8.0 nM for Cr3+; 25–400 nM for Cr3+;
and assisted silver [131]
Deep yellow to colorless water samples 0.27 µM for Cu2+ 0.3–10 µM for Cu2+
Cu2+ nanoplates
(A390) for Cu2+
Dark brown to light
brown for Fe3+;
1.69 ppb for Fe3+;
Dark brown to white for
Fe3+, Cu2+, Environmental 3.18 ppb for Cu2+;
Ag@AgCl NPs Cu2+; 0–100 ppb [132]
and Cr6+ water samples 5.05 ppb for
Dark brown to orange
Cr6+
for Cr6+
(A400–500)
Claret-red to gray Environmental
Pb2+ G-AuNPs 1.07 µM 10–80 µM [133]
(A530) water samples
L-Cysteine
functionalized Darker blue color of TMB
Hg2+ graphene oxide oxidation products Water 7.6 µgL−1 0–200 µgL−1 [134]
nanoarchitectonics (A652)
CGO
Graphene oxide Yellow to colorless Environmental
Hg2+ 0.64 nM 10–100 µM [135]
stabilized AgNPs (A400) water samples
Aptamer-modified Blue to red Environmental 8.2 × 10−10 M ~ 6.2 ×
Hg2+ 4.9 × 10−11 M [136]
cationic AuNPs (A560/A700) water samples 10−8 M
Cu@Ag NPs, stabilized Yellow to pink
Hg2+ Aqueous solutions 5 × 10−6 M Not reported [137]
with Citrus paradisi peel (A492/A411)
Bright red to purple for
Hg2+ and 2-thiazoline-2-thiol
(Hg2+); bright red to blue Water samples ~100 ppb 0.1–10µM [138]
Pb2+ functionalized AuNPs
for (Pb2+) (A521)
ssDNA (Hg) 3.8 µgL−1 for Hg2+
Hg2+ and Light green-yellow
functionalized Water samples and 2.4 µgL−1 for Not reported [139]
Cd2+ (A450)
Mn3O4NPs Cd2+
Brownish-yellow to pale
Cd2+ and Environmental
PC-Ag NPs yellow 0.2 nM 0.05–100 µM [140]
Ni2+ water samples
(A445)
Biological Samples
Acyclovir stabilized,
Yellow to greyish Human blood
Hg2+ silver nanoparticles AC- 0.00035 mM Not reported [141]
(A404) plasma
AgNPs
Silver nanoparticles on
Dark blue color of TMB
covalent organic 0.050–10
Hg2+ oxidation products Human blood 3.7 nM [142]
frameworks µM
(A652)
COF-Ag nanozymes
Polyethylene glycol-
capped gold Wine red to blue Human tissues
As3+ 2.9 ppm 0.1–10 ppm [143]
nanoparticles (PEG- (A612/A521) (viscera)
AuNPs)
Sensors 2023, 23, 9080 13 of 27

As3+ aptamer
functionalized
Blue to red
As3+ positively charged gold Urine 0.41 ppb 2–40 ppb [144]
(A680/A526)
nanoparticle.
As 3+ -apt- +AuNPs
Consumables
L-Cysteine modified
Red to blue
Cd2+ gold nanoparticles Milk Not reported Not reported [145]
(A520)
AuNPs
Film of Tapioca starch
Red-purplish to grey
Cd2+ and gold nanoparticles Fish 13.1 mmolL−1 6–12 mmolL−1 [146]
(A620)
Ts-AuNPs

3.1. Colorimetric Nanosensors for Detecting Heavy Metal Ions in Environmental Samples
3.1.1. Detection of Cu2+ Ions
Copper is a heavy metal with a significant role in environmental pollution due to its
abundant presence in aquatic environments (e.g., marine and freshwater habitats) and
industrial runoffs. It is toxic at high concentrations to all living species. Ghasemi and
Mohammadi [130] developed a novel thiazolylazopyrimidine-functionalized TiO2
nanosensor (TiO2-TAP) to detect Cu2+ in aquatic samples. They synthesized
thiazolylazopyrimidine (TAP), an azo ligand that contained N, S, and O functional groups
as binding sites. The TAP ligand has the azo chromophore (N=N), which can generate a
color and form a stable complex with Cu2+ grounded on the charge-transfer transduction
process during detection. The ligand was activated with epoxy, a surface modifier, and
reacted with titanium dioxide nanoparticles to form TiO2-TAP NPs. The nanosensors were
assessed by various characterization techniques. An aqueous solution of TiO2-TAP NPs
was then used to detect Cu2+ ions by examining its ability to adsorb these ions from the
aqueous media. Due to surface complexation, the nanosensor solution turned from yellow
to red within a few seconds upon adsorption of Cu2+ ions. The maximum absorbance of
the resulting complex solution was 536 nm. In addition, the linear range for detecting Cu2+
ions in aqueous media was between 0.01 and 12.5 µM, and the limit of detection (LOD)
was 2.51 nM. The optimum adsorption of Cu2+ ions to TiO2-TAP NPs from tap water,
seawater, and well water occurred at pH 5 and was selective. Moreover, the sensor’s
response time was short, with a high adsorption efficiency towards Cu2+ (after 30 min, 93%
of the copper ions were adsorbed). Furthermore, the authors report that the design and
fabrication of this sensitive nanosensor were straightforward and inexpensive [130].

3.1.2. Detection of Cr3+ and Cu2+ Ions

Wang and coworkers [131] developed multi-functional iodide-assisted silver
nanoplates by coating the surface with citrate and iodide ions for the selective and
sensitive colorimetric detection of chromium (III) and copper (II) ions in tap and lake
water samples, respectively. The detection of Cr3+ by citrate-capped silver nanoplates was
based on the aggregation of silver nanoplates due to the affinity of Cr3+ ions for the
carboxylate groups of citrates, which cause the solution’s color to change from deep
yellow to purple and finally to colorless. The synthesized colloidal silver nanoplates were
evaluated by several characterization techniques. When Cr3+ ions were added to the
citrate-functionalized silver nanoplates, the nanosensors’ hydrodynamic diameter
increased from ~35 to ~379 nm. Furthermore, upon adsorption of Cr3+ to the surface of the
silver nanoplates, the zeta potential value decreased as the Cr3+ concentration increased,
which in turn triggered aggregation. The authors also found that the Cr3+ ions formed a
coordination complex with the citrate-capped silver nanoplates, thereby neutralizing the
surface charge. This increased the dispersion force between the Cr3+ ions and the
nanosensor, causing aggregation. The silver nanoplates had a maximum absorbance of
390 nm. However, as Cr3+ ions were added, this peak decreased while a new absorption
Sensors 2023, 23, 9080 14 of 27

peak at 520 nm arose due to silver aggregation. At the same time, the authors noticed a
color change (deep yellow to purple) in the solution. The linear range to detect Cr3+ based
on A390/A520 was between 25 and 400 nM, and the LOD was calculated to be 8.0 nM. The
colorimetric detection of Cu2+ by iodide-assisted silver nanoplates was based on
fusion/oxidation etching of the silver nanoplates, causing the solution to change from
deep yellow to colorless as the Cu2+ concentration increased. The morphology of the fused
iodide silver nanoplates was assessed using TEM. When Cu2+ ions were added to the
iodide-assisted silver nanoplates, the nanosensors’ hydrodynamic diameter increased
from 68 to 133 nm. The zeta potential also increased, indicating that the surface charge of
the silver nanoplates increased due to the fusion procedure and oxidation etching. The
detection mechanism of Cu2+ was based on the adsorption of I− onto the surface of the
silver nanoplates and then the fusion/oxidation etching process, which was as follows:
Cu2+ oxidizes I− to I2 through the intermediate product CuI. Then, the formed I2 oxidizes
silver on the silver nanosensors to AgI, changing from deep yellow to colorless as the Cu2+
concentration increases. The linear range for the detection of Cu2+ was measured at A390
and was between 0.3 and 10 µM, and the LOD was 0.27 µM. The researchers also indicated
that the design of the iodide-assisted silver nanoplates was easy and fast [131].

3.1.3. Detection of Fe3+, Cu2+, and Cr6+ Ions

In another study, Augen et al. [132] used green algae to synthesize Ag/AgCl
nanoparticles (NPs) for colorimetric detection of Fe3+, Cu2+, and Cr6+ ions. Seaweed extract
was used as a stabilizing and reducing agent as it contains an abundance of biomolecules
(e.g., polysaccharides, proteins, lipids, polyphenols, and carotenoids). Moreover, green
algae is known to be a source of Cl− ions. During the synthesis of Ag/AgCl, the seaweed
extract was combined with an AgNO3 solution (1:9, v/v) at 95 °C, which led to the
formation of AgCl. Subsequently, the AgCl was stabilized by the organic compounds in
the green extract. At the same time, some other Ag+ ions were reduced to Ag0 by reducing
biomolecules (e.g., chlorophyll and phenols) in the seaweed extract. The precipitation of
AgCl occurred at a high temperature, which increased its solubility, leading to its
decomposition into its ions. In turn, these silver ions were also reduced to metallic silver.
This change in equilibrium led to the formation of Ag@AgCl NPs. These green
nanoparticles were evaluated using several characterization techniques. The Ag@AgCl
NPs were spherical and ranged between 4 and 10 nm. The synthesized nanosensors were
dark brown and had a maximum absorbance peak between 400 and 450 nm due to surface
plasmon resonance (SPR) formation. The Ag@AgCl NPs had negatively charged surfaces
because of the functional groups (amino, carboxyl, and hydroxyl) in the green algae,
which led to the aggregation of the nanoparticles upon the addition of the metal ions.
Upon adding Fe3+ and Cu2+ metal ion solutions to the nanosensors, the characteristic SPR
band of Ag@AgCl NPs disappeared. Furthermore, the metal ion absorbance peak was
slightly around the Ag@AgCl NPs absorbance peak with a shift toward the blue.
However, for Cr6+ metal ions, the authors noticed a decrease in the SPR peak of
Ag@AgCl NPs with a redshift. In addition, a peak at 390 nm appeared for Cr6+ ions. Results
showed that these Ag@AgCl NPs could detect the metal ions by forming different colors.
Solutions of Ag@AgCl NPs turned in the presence of Fe3+, Cu2+, and Cr6+ ions from dark
brown to light brown, white, and orange, respectively. The color intensity changes and
the amount of aggregation of the nanoparticles were found to be dependent on the metal
ions’ concentration. The LOD values of the metal ions Fe3+, Cu2+, and Cr6+ were 1.69, 3.18,
and 5.05 ppb, respectively. The linear range for each metal ion was reported to be between
0 and 100 ppb. This eco-friendly synthesis method for these biogenic Ag@AgCl NPs was
found to be inexpensive. Moreover, these nanosensors were highly sensitive for the
concurrent colorimetric detection of Fe3+, Cu2+, and Cr6+ ions in wastewater [132].
Sensors 2023, 23, 9080 15 of 27

3.1.4. Detection of Pb2+ Ions

Li et al. [133] developed a plasma-based system for the instant and continuous green
synthesis of glucose-functionalized gold nanoparticle (G-AuNPs) sensors for the
colorimetric detection of Pb2+ ions. The authors utilized a one-pot microplasma system
using plasma electrons as reducing agents to add Pb2+ functionalized groups (e.g.,
hydroxyl and carboxyl) from glucose to the surface of AuNPs, forming G-AuNPs. Thus,
in the presence of Pb2+ ions, a G-AuNPs/Pb2+ complex was produced, causing a shift in the
SPR and making colorimetric detection of Pb2+ ions possible. They also developed an
advanced microfluidic plasma system for the continuous synthesis of G-AuNPs and
simultaneous colorimetric detection of lead (II) ions within half a minute. The prepared
functionalized gold nanosensors were evaluated using various characterization
techniques. The absorption spectrum of the G-AuNPs showed an SPR peak at 530 nm, and
the color of this nanosensor solution was claret-red. When aqueous Pb2+ ions were added
to the G-AuNPs, an additional absorption peak appeared at 767 nm, while the one at 530
nm significantly decreased. At the same time, the color of the G-AuNPs changed to gray,
indicating the formation of a G-AuNPs/Pb2+ complex as nanoparticle aggregation
occurred. Results showed that Pb2+ ions form a coordination complex with the hydroxyl
and carboxyl groups on the G-AuNPs surface. The nanosensor was highly sensitive and
selective toward the in situ detection of Pb2+ ions. The LOD was 1.07 µM, and the linear
range was between 10 and 80 µM [133].

3.1.5. Detection of Hg2+ Ions

Tian and coworkers [134] developed L-cysteine functionalized graphene-oxide
(CGO) nanosheets as nanosensors for the colorimetric detection of mercury ions (Hg 2+) in
water samples. This metal-free chemical sensor was greenly synthesized at room
temperature. The colorimetric detection of trace Hg2+ was based on the presence of sulfur
and oxygen groups on the CGO that served as active sites for binding Hg2+. The interaction
of the CGO, colorimetric substrate 3,3ꞌ,5,5ꞌ- tetramethylbenzidine (TMB), and Hg2+ was
investigated and it was revealed that competitive adsorption existed between Hg2+ ions
and TMB over the CGO, with the Hg2+ ions hindering the TMB from binding on the CGO.
This facilitated the oxidation of TMB by peroxide, producing more colored oxidation
products (darker blue), from which the colorimetric sensing of Hg2+ could be reached with
good detection. A high efficiency and sensitive response to Hg2+ was demonstrated, with
a detectable range of 0–200 µgL−1 and a detection limit of 7.6 µgL−1. This CGO-based
colorimetric sensor also offered high selectivity for the target Hg2+ ions, with no detectible
disturbance from other co-existing metal ions [134].
In a related study, graphene oxide (GO) stabilized silver nanoparticles (AgNPs) were
created for the colorimetric detection of trace Hg2+ in environmental water samples [135].
Sugar beet bagasse, an agro-industrial waste product, was carbonized by combustion, and
the recovered graphite powder was used to synthesize graphene oxide. The graphene
oxide was then applied as a stabilizer of the silver nanoparticles. The Ag-GO nanoparticles
(AgNPs) were prepared by an in situ reduction reaction of Ag+, which resulted in a yellow
solution (λmax 400 nm) of AgNPs. The sensor was then used to detect trace Hg2+. Here, the
mechanism was based on an amalgam reaction between AgNPs and Hg2+ and resulted in
an observed color change of the sensor solution from yellow to colorless. Their produced
sensor exhibited practical application potential, with good sensitivity and selectivity to
Hg2+ in the presence of other ions. A linear range of 10–100 µM and a detection limit of
0.64 nM were reported [135].
Qi et al. [136] reported a practical and sensitive aptamer-based colorimetric assay for
Hg2+ by observing (visual and spectrum detection) changes in cationic gold nanoparticles
(AuNPs). The observed changes were based on the affinity interaction of the nanoparticles
with the mercury aptamer in the presence or absence of Hg2+. This investigation
highlighted the progress that has been made with aptamer recognition for analysis and
Sensors 2023, 23, 9080 16 of 27

detection, as well as AuNP colorimetric analysis using aptamer recognition technology.

Cationic AuNPs were used to distinguish the conformation formed by the affinity action
of the aptamer and mercury (T-Hg-T) from the original conformation of the aptamer
without mercury. This approach was taken to avoid any indirect responses that would
have been induced by salt addition if the alternate anionic nanoparticles had been used.
Their results showed that in the absence of Hg2+, the aptamer had its original single-
stranded DNA conformation and would easily wrap around the surface of the AuNPs,
causing them to agglomerate. Here, the resulting cationic AuNP solution was blue in
appearance. Conversely, in the presence of Hg2+, due to high-affinity interactions with
their aptamers, a solid T-Hg-T conformation was formed. The rigid aptamers were then
unable to wrap onto the cationic AuNPs, causing the AuNPs to remain in their dispersed
state, and the solution appeared red. Experimental results showed that Hg2+ concentration
ranges from 8.2 × 10−10 to 6.2 × 10−8 M had high sensitivity correlation with an absorbance
ratio of (A650/A700) for detecting Hg2+ with a limit of detection of 4.9 × 10−11 M. This aptamer–
AuNP system was also selective for Hg2+ when applied to actual environmental samples.
The advantage here is that once the aptamer of any polluting metal is used, then this
presented method could be applied to detecting that heavy metal. Thus, a practical
colorimetric analysis involving the simple synthesis of metal-specific probes was
illustrated [136].
Bimetallic nanoparticles can also find application as colorimetric sensors. For
example, Kheibarian and colleagues synthesized Cu@Ag core-shell NPs using the
aqueous extract Citrus paradisi peel as a reducing and stabilizing agent [137]. They
successfully used the system for the selective colorimetric detection of Hg2+ ions in an
aqueous solution. Their reasoning for the copper core with a silver shell nanoparticle
design was to improve stability and copper core functionality. Additionally, the
flavonoids and polyphenols in the Citrus paradisi peel served as reducing and stabilizing
agents in synthesizing the bimetallic nanoparticles. The coupling of these two metals
forms bimetallic nanoparticles with improved surface plasmon resonance. Ultraviolet–
visible (UV-Vis) characterization of the synthesized mixture showed a Cu@Ag NPs
absorbance band at 411 nm, indicating that the Cu-NPs were coated with Ag-NPs; several
other characterization techniques were also used to confirm the synthesis of the intended
nanoparticle design. When Hg2+ ions were added to the Cu@Ag NP solution, the color of
the solution changed from yellow to pink, with the absorbance band at 411 nm decreasing
and a second absorption band appearing at 492 nm. Their sensitivity and selectivity
analysis of the colorimetric sensor to other metals, including Ni2+, Cd2+, and Pb2+, showed
that these metals did not interfere with the detection of Hg2+ ions. The UV-Vis absorbance
of Cu@AP NPs with different concentrations of Hg2+ ions gave good absorbance ratio
(A492/A411) correlations, with a detection limit of 5 × 10−6 M [137].

3.1.6. Detection of Hg2+ and Pb2+ Ions

Chadha and coworkers reported the synthesis of a novel 2-thiazoline-2-thiol (TT)
functionalized gold (Au-TT) nanosensor for the colorimetric detection of Hg(II) and Pb(II)
ions in aqueous solutions [138]. Colloidal AuNPs were prepared and functionalized by
adding different concentrations of TT to the nanoparticles. Observed color changes of the
Au-TT nanoprobe colloidal solution ranged from bright red to purple in the presence of
Hg(II) ions, to bright red to blue in the presence of Pb(II) ions. The absorption spectrum
of the Au-TT sensor showed a bulk-like surface plasmon resonance (BL-SPR) band with a
maximum at A521. There was a slight increase in the band absorbance when an Hg(II)
solution was added to the nanosensor. However, when a Pb(II) solution was added to the
probe, not only did the BL-SPR band decrease in intensity, but a new shoulder/red-shifted
peak was also observed. Furthermore, the investigators gave characterization evidence to
show that the observed color changes resulted from differences in the binding affinities of
the metal ions towards the active binding sites of TT. The Au-TT nanosensor was also
tested for its selectivity and specificity using various metal ions and actual samples from
Sensors 2023, 23, 9080 17 of 27

different water sources. The sensor was shown to be selective towards Hg(II) and Pb(II)
ions, with high specificity towards Pb(II) ions in the presence of all other metal ions, at a
limit of detection of approximately 100 ppb [138].

3.1.7. Detection of Hg2+ and Cd2+ Ions

Wang et al. [139] developed a rapid and convenient method to detect Hg(II) and
Cd(II) ions in water samples. They prepared a colorimetric sensor that utilized an aptamer
made from a thymine (T) rich sequence (ssDNA (Hg)) to regulate the oxidase-mimicking
activity of Mn3O4-NPs. In an acidic solution, the chromogenic substrate 3,3ꞌ,5,5ꞌ-
tetramethylbenzidine (TMB) is oxidized by Mn3O4-NPs to give a yellow-colored solution.
The aptamer served dual purposes. Firstly, the ssDNA (Hg) sequence was absorbed onto
the surface of certain shaped Mn3O4- NPs, limiting their catalytic oxidation of TMB. This
led to a color change of the solution from yellow to light green, and a smaller absorption
peak was observed at 450 nm. Secondly, in the presence of Hg(II) and Cd(II) ions, the
ssDNA (Hg) sequence would bind to these metals and no longer inhibit the oxidase-
mimicking activity of the Mn3O4-NPs. The color of the sensing solution was then restored
to yellow, with the increase in absorbance at 450 nm corresponding to the amounts of
heavy metals present. The method was reported to be cost-effective, easy to use, and
allowed Hg(II) and Cd(II) to be detected at concentrations as low as 20 µgL−1, with
detection limits of 3.8 µgL−1 of Hg(II) and 2.4 µgL−1 of Cd(II), respectively. The
investigators of this study believe that the method could be extended to detect other
metals of interest by simply incorporating target-specific aptamers [139].

3.1.8. Detection of Cd2+ and Ni2+ Ions

In a green synthesis method, Mohammadzadeh et al. [140] used a green walnut husk
(GWH) extract for the synthesis of phenolic capping silver nanoparticles (PC-Ag NPs) to
colorimetrically detect Cd2+ and Ni2+ ions in surface water and groundwater samples. In
this investigation, the phenolic content of the Persian walnut (Juglans regia L.) extract was
utilized as a reducing and stabilizing agent to synthesize Ag NPs. The PC-Ag NPs were
prepared by adding GWH extract to an AgNO3 solution, in which the phenolic
compounds in the extract were adsorbed on the surface of Ag+ ions and stabilized the
formed nanoparticles. The LSPR absorbance band for the PC-Ag NPs was 445 nm. The
synthesis of these nanosensors was confirmed when the solution turned from pale yellow
to brownish yellow. The optical and chemical properties of the synthesized PC-Ag NPs
were assessed using various characterization techniques. The colorimetric sensing
mechanism was based on the reaction of the polyphenol functional groups (i.e., carboxyl
and hydroxyl) of GWH on the surface of the nanosensors with Cd2+ and Ni2+ ions. In turn,
this reaction led to the formation of chelate complexes with the metal ions, causing
aggregation (with Cd2+ and Ni2+ ions) and sedimentation (with only Ni2+) of the
nanoparticles. A visual color change from brownish yellow to pale grey was also seen
when Cd2+ and Ni2+ ions were added to the nanosensors. Moreover, with increasing
concentrations of Cd2+ and Ni2+ ions in the PC-Ag NP solutions, the LSPR absorbance band
gradually decreased. Likewise, a gradual redshift was seen due to the aggregation of the
PC-Ag NPs. The detection limit for both metal ions was 0.2 nM, and the linear range was
between 0.05 and 100 µM. The sensor was found to have good selectivity and sensitivity
at an optimized pH of 6 [140].

3.1.9. Detection of Various Heavy Metal Ions

In a similar green synthesis investigation to Augen et al. [132] and Mohammadzadeh
et al. [140], Sharma and coworkers [147] synthesized pectin-functionalized nanoparticles
(P-AgNPs) using a microwave-assisted method. Likewise, in this study, pectin was used
as a reducing and stabilizing agent during the synthesis of the AgNPs. The pectin-
functionalized nanoparticles were evaluated by various characterization techniques, and
Sensors 2023, 23, 9080 18 of 27

they had a maximum absorbance of 409 nm. Subsequently, the synthesized P-AgNPs were
utilized for the colorimetric detection of a broad range of metal ions (Fe(II), Mn(II), Cr(III),
Cr(VI), and As(V)) in aqueous solutions. When an aqueous colloidal P-AgNP solution was
added to water samples containing Fe(II) and Mn(II) ions, the solution’s color changed
from light yellow to black and dark brown, respectively. The solution’s color intensity
depended on the concentration of these metal ions in the water. At low concentrations of
Fe(II), the LSPR peak of the P-AgNPs shifted to 440 nm, whereas at high concentrations
of this metal ion, new bands were formed at 375 and 475 nm. The researchers found that
adding Mn(II) ions changed the LSPR band of P-AgNPs while slightly increasing the
absorbance. However, high concentrations of Mn(II) ions led to distortion of the
absorption peak due to agglomerate formation. No significant color change was observed
when water samples containing a low concentration of Cr(III) ions were mixed with the
colloidal P-AgNP solution. Conversely, at medium-to-high concentrations (40–90 µM) of
Cr(III) ions, the solution’s color changed from light yellow gradually to reddish brown
and finally to intense brown at 100 µM. Likewise, these visual color changes with a Cr(III)
concentration increase correlated to an absorption increase of the LSPR peak. The authors
also observed a Cr(III) concentration of 40–100 µM, a downward peak shift seen at 400
nm, and, between 70 and 100 µM, an additional peak at 479 nm. On the other hand, adding
an aqueous Cr(VI) ion solution to a colloidal P-AgNP solution led to a slight blue shift in
the LSPR peak, which became higher as the Cr(VI) concentration increased. The P-AgNP
solution changed from light yellow to pale yellow. It was found that the color intensity
was not concentration dependent. The authors suggested this detection pattern could be
helpful for the preliminary screening of Cr(III) and Cr(VI) ions. When As(V) ions at low
(2–25 µM), medium (35–50 µM), and high (>50 µM) concentrations were mixed with P-
AgNPs, a color change from light yellow to red, brown, and light yellow (no color change)
was observed, respectively. The As(V) caused in the presence of P-AgNPs a blue shift of
only 1 nm. At low and medium concentrations of As(V) ions, there was a direct
proportional relationship with the absorbance, indicating a complex formation between
As(V) ions and P-AgNPs. However, at high concentrations of As(V) ions, there was an
inversely proportional relationship with the absorbance. In this study, the researchers
found that the variations in color and LSPR absorption fingerprint of P-AgNPs were due
to the formation of nanoparticle aggregates with the added metal ions. Results show that
the pectin functional groups (e.g., carboxyl and hydroxyl) on the nanoparticles’ surfaces
formed a complex with the heavy metal ions through metal–ligand interaction. This
caused the dispersed P-AgNPs to become aggregated, causing the nanoparticles to be
closer to each other and ultimately resulting in a change in peak position and color change.
The data from this investigation indicate the potential use of these P-AgNP sensors as a
screening and detection method for various metal ions. This colorimetric detection
method was straightforward, fast, and sensitive [147].

3.2. Colorimetric Nanosensors for Detecting Heavy Metal Ions in Biological Samples
Colorimetric techniques have become popular recently because of on-the-spot
detection, sometimes with the naked eye and without sophisticated instrumentation.
Ullah et al. [141] synthesized highly sensitive, acyclovir-stabilized silver nanoparticles
(AC-AgNPs) that were selective for sensing Hg2+ ions and found application in detecting
Hg2+ ions spiked in human blood plasma samples. The AC-AgNPs were synthesized using
a chemical reduction method, where a color change from colorless to yellow indicated
successful synthesis of the AC-AgNPs. The role of the acyclovir was to stabilize Ag+ and
reduce it by donating an electron pair. The presence of functional groups on the stabilizer
also served to enhance the binding of Hg2+ onto the AgNPs surface. The synthesized AC-
AgNPs were initially characterized using UV-Vis spectroscopy at a wavelength of 404 nm,
along with other characterization techniques. The AC-AgNPs were small (44.1 nm) with
uniform morphology and size distribution and had a zeta potential of −17.4 mV. The AC-
AgNPs, when mixed with Hg2+ ions, showed variations in surface plasmon resonance, and
Sensors 2023, 23, 9080 19 of 27

gave an absorption spectrum with hypochromic and hypsochromic shifts and observable
color change of the sensor solution from yellow to greyish. Data from their experiments
suggested a 1:2 binding stoichiometry between AC-AgNPs and Hg2+ ions, with a detection
limit of 0.00035 mM. Moreover, the nanosensor was selective for Hg2+ ions even in the
presence of interfering metal ions (Ca2+, Ba2+, NH4+, Cu2+, Pb2+, Co2+, Cr2+, Al3+, Pb2+, Fe2+,
Ni2+) in various samples. Thus, the results of this study showed the potential of the
designed colorimetric nanosensor for the selective and easy detection of Hg2+ in different
media [141].
In a related study, Liu et al. [142] developed a colorimetric method that was highly
selective and sensitive to Hg2+ ions and successfully used it to detect mercury in human
blood. They fabricated covalent organic frameworks (COFs) and grew noble silver
nanoparticles (Ag-NPs) onto the COF surfaces in situ, via a one-step chemical reduction
method, to yield COF-Ag nanozymes. Characterization with a transmission electron
microscope (TEM) showed the COF-Ag nanozymes formed a monodispersed hierarchical
flower-like structure with uniform nanoparticles on the surface of the pores of the COFs.
The COF-nanozymes possessed oxidase-like catalytic activity that was enhanced in the
presence of Hg2+ ions, forming Ag-Hg alloys. This oxidase-like catalytic activity was
observed with the colorimetric substrate 3,3′,5,5′-tetramethylbenzidine (TMB): in the
presence of Hg2+ ions the oxidase activity of the COF-Ag nanozyme with TMD resulted in
a blue colored solution, while in the absence of Hg2+ ions the solution remained colorless.
The COF-Ag nanozymes with and without mercury were characterized by UV-Vis
spectroscopy, where COFs were taken as a control. Observations showed that adding Hg2+
ions enhanced the absorbance of COF-Ag nanozymes, which was postulated to be due to
the scattering effect of the formed Ag-Hg alloys. Detection of different concentrations of
Hg2+ ions spiked in blood samples gave favorable recoveries and proved the reliability of
the colorimetric method for determining Hg2+ ions in blood samples; a linear
concentration range from 0.050 to 10.0 µM and a limit of detection of approximately 3.7
nM was reported for this colorimetric method. It was also shown that other measured ions
(example Fe3+, Cu2+, Ca2+, Cd2+, Zn2+, Pb2+, Cr3+, I−, SrO32−, S2−) had negligible influence on
the catalytic activities of COF-Ag nanozymes, when compared to Hg2+, thus confirming
the high detection selectivity of the reported colorimetric method for Hg2+ ions [142].
A novel process towards the detection of Arsenite (As(III) in tissue samples (aka
viscera/internal organs) using polyethylene glycol capped gold nanoparticle (PEG-
AuNPS) nanocomposites was reported by Shalvi et al. [143]. In the study, the PEG-AuNPs
were prepared and characterized using several characterization techniques. It was shown
that electrostatic interaction caused the aggregation of As III ions on binding with the
nanocomposites, which resulted in a color change from wine-red to blue. An optical hand-
held device was fabricated in-house and used to quantify trace amounts of As III ions in
the samples based on absorbance at 612/521 nm. The development and integration of the
hand-held device with the nanocomposites facilitated the on-the-spot quantification of As
III ions in tissue samples. The sensing capability of the hand-held device using the PEG-
AuNPs showed good linearity (0.1–10 ppm) and correlation when compared with
standard methods. The developed PEG-AuNPs were reported to be sensitive and selective
in detecting As III ions in the presence of interfering components (for example Ca2+, Cd2+,
Cu2+, Na+, Ni2+, Al3+, Hg2+, Mn2+, Mg2+, and Zn2+), with their hand-held device having a
detection limit in tissue samples of 2.9 ppm [143].
In a separate investigation by Zhang et al. [144], AuNPs functionalized with
cysteamine aptamer were used to detect As(III) ions in artificial urine. They developed a
dual-mode (dispersion and aggregation) colorimetric method for the determination of
As(III) ions that was based on specific recognition and electrostatic interaction between
As III ions, As III aptamer (As III-apt), and positively charged gold nanoparticles
(+AuNPs). The wine-red colored +AuNPs were prepared and characterized. Following
that, the negatively charged AsIII-apt solution was prepared and used to functionalize the
+AuNPs. The aptamer solution served to regulate the aggregation and dispersion of the
Sensors 2023, 23, 9080 20 of 27

+AuNPs, via electrostatic interactions between the nanoparticles and the aptamer. The
color of the +AuNP solution changed from red to blue to red as the concentration of the
AsIII-apt increased. The absorbance of the reaction solutions was measured at 680 nm
(A680), which calculated the relative amounts of aggregated +AuNPs, as well as at 526 nm
(A526), which determined the relative amounts of dispersed +AuNPs. Thus, the ratio of
A680/A526 represented the ratio of aggregated to dispersed +AuNPs. Final concentrations of
8 nM of As III-apt (for the dispersed mode) and 15 nM (for the aggregated mode) were
used to determine As(III) ions in natural samples, as well as artificial urine. Thus, in this
biosensor, the aggregation of +AuNPs resulted when the aptamer concentration was low
(8 nM). Then, as As(III) ions were introduced, a complex formed between the As III-apt
and As III ions. The depletion of the aptamer caused the +AuNPs to continue to be
dispersed in the solution. Conversely, with increased concentration of As III-apt (8–15
nM), electrostatic interactions caused the +AuNPs to remain dispersed in the detection
system. Then, as As III ions were introduced, the As(III) ions would complex with the AS
III aptamer, depleting the amount of aptamer adsorbed onto the surface of the +AuNPs,
causing them to aggregate. In this study, the LOD for detecting As(III) ions in urine using
the biosensor in aggregation mode was reported to be 0.41 ppb with a linear range of 2–
40 ppb (R2 = 0.996). In addition, the authors reported that their use of +AuNPs and aptamer
proved to be advantageous, as the detection process and detection time were simplified
and shortened, when compared to their previous methods which used negatively charged
AuNPs, cationic polymer, or salts and aptamer [144].

3.3. Detection of Heavy Metal Ions in Consumable Products

The colorimetric determination of heavy metals using nanosensors has also found
application in the food industry. The metal ion cadmium is a highly toxic, carcinogenic
contaminant that adversely affects human health [148]. Non-industrial exposure may arise
from cigarette smoke and food (via soil and water contamination). Milk and dairy
products can become contaminated with cadmium ions from either adulteration or
dilution with water [149]. Therefore, an accurate and selective method for detecting and
monitoring this element is essential. Sonia and Raman [145] developed an L‐Cysteine
modified gold nanoparticle (AuNP)-based colorimetric assay technique for detecting the
toxic metal ion of cadmium in milk samples. They described their technique as a simple
and low-cost alternative compared to other spectroscopy-based methods. The authors
reported that synthesized colloidal AuNPs possessed strong SPR absorptions with high
extinction coefficients in the visible range; they believe these properties depend on the
shapes and sizes of the AuNPs, the dielectric constant of their surrounding aqueous
media, and interactions with neighboring particles. In their study, 24 nm spherical AuNPs
were prepared from reducing gold (III) chloride trihydrate with sodium tri-citrate. The
AuNPs were later functionalized with L‐cysteine. Their synthesized L‐cysteine AuNPs
were dark red in color, spherical when viewed under a transmission electron microscope
(TEM) and had the strong ability to form aggregates with toxic metal ions, leading to a
color change. The L‐cysteine acted as a target-specific ligand, facilitating binding to target
metal ions. When metal ions (Cd2+) were introduced, they would bind through the ligands
of multiple AuNPs, inducing nanoparticle aggregation, which resulted in a new
ultraviolet–visible band at 520 nm and an observable color change of the red AuNPs into
a deep blue [145].
Vonnie et al. [146] also developed a sensitive, simple, uncomplicated, and
environmentally friendly colorimetric detection method using a film of tapioca starch and
gold nanoparticles (TS-AuNPs), which was selective for cadmium ions (Cd2+) in fish.
Significant absorbance was observed at a wavelength of 620 nm when a cadmium solution
was added to the sensor. Moreover, the TS-AuNPs showed increased response to Cd2+
when compared to other metal ions (Hg2+, Ni2+, Fe2+, Pb2+ and Cu2+). The tapioca starch (TS)
thin film was used as the colorimetric reagent carrier, which allowed for on-site detection.
The AuNP aggregates were produced from the reaction of chloroauric acid and sodium
Sensors 2023, 23, 9080 21 of 27

citrate. The subsequent formation of negatively charged AuNPs on the surface of the TS
thin film was stabilized by citrate ions, which allowed them to remain dispersed in the
solution. The detection process was based on the affinity level of the heavy metal ions
(Cd2+) and their ability to exert an attractive force on the negative surface of the Au-NPs.
The detection mechanism was based on aggregate formation between the AuNPs and
cadmium, which resulted in a color change of the solution from red to purplish grey. The
reported UV-Vis curves of the colorimetric response of the AuNPs and cadmium showed
linearity in the cadmium concentration range from 6 mmol.L−1 to 12 mmol.L−1 (R2 = 0.9935)
and an LOD of 13.1 mmol.L−1. Furthermore, the edible parts of seven deep-sea fish species
were tested (Thannus obesus, Scomberomorus commerson, Euthynnus affinis, Nemipterus
furcosus, Selar crumenophthalmus, Pracanthus lovetii, and Megalaspis cordyla). The results
showed all of them to be contaminated with Cd2+ at levels that were reported to be higher
than Cd2+ permissible values [146].

4. Conclusions and Future Directions

This review highlighted the innovations and advancements in electrochemical and
colorimetric nanosensors for heavy metal ions in a variety of samples of ecological,
environmental, biological, and consumable interest. The quality and high volume of
published articles in high-impact journals demonstrate a continued interest and the
critical need to develop an analytical protocol for rapidly detecting heavy metal ions to
prevent environmental contamination and heavy metal ion poisoning to ensure public
health safety. Notable achievements and progress have been made in developing sensors
capable of accurate and reproducible heavy metal ion detections at trace and ultra-trace
concentrations. Nonetheless, sensitivity, selectivity, specificity, and interference remain
challenging for several available sensors. Considerable efforts will be devoted to
developing improved electrochemical and colorimetric nanosensors with better
selectivity, sensitivity, and specificity to facilitate reliable and expanded heavy metal ion
detections. Specifically, efforts will be dedicated to the instrumental design and
development of more portable electrochemical sensors based on graphene, carbon
nanotubes, nanostructures, carbon dots, nanomaterials, and metal–organic frame sensors
to promote selective and specific heavy metal ion detections. The development of portable
colorimetric sensors that will promote fast screening and visual detection of heavy metal
ions will continue to be an active research area in the coming years. Improved technology
and smartphone access will enable the wide application and development of smartphone-
based sensors that will facilitate rapid, in situ, and on-site detection of heavy metal ions.
Several low-cost and disposable paper-based sensors will be developed that will facilitate
in situ and field detection of heavy metal ions. Microfluidic and microchip sensors will
generate more research interest to promote rapid arrays and simultaneous heavy metal
ion detections. Using functionalized gold nanoparticles for fiber-optics surface plasmon
resonance for heavy metal ion sensing will attract greater interest. In addition, more
articles will report on using automated and robotic sensors for heavy metal ion detections.

Funding: This research received no external funding.

Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data are contained within the article.
Conflicts of Interest: The authors declare no conflict of interest.

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