Chemical Engineering Journal Advances 11 (2022) 100353

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Chemical Engineering Journal Advances

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Photocatalytic nanomaterials: Applications for remediation of toxic

polycyclic aromatic hydrocarbons and green management
Vishal Dutta a, Jyothis Devasia b, Ankush Chauhan c, Jayalakshmi M b, Vasantha V L d,
Ayush Jha e, Aatika Nizam b, *, Kun-Yi Andrew Lin f, Suresh Ghotekar g, *
a
Advanced School of Chemical Sciences, Shoolini University, Solan Himachal Pradesh, 173212, India
b
Department of Chemistry, CHRIST (Deemed to be University), Bangalore Karnataka, 560029, India
c
Chettinad Hospital and Research Institute, Chettinad Academy of Research and Education, Kelambakkam, Kanchipuram Tamil Nadu, 603103, India
d
Department of Life Sciences, CHRIST (Deemed to be University), Bangalore, Karnataka 560029, India
e
University Institute of Biotechnology, Chandigarh University, Gharuan, Punjab 140413 India
f
Department of Environmental Engineering & Innovation and Development Center of Sustainable Agriculture, National Chung Hsing University, 250 Kuo-Kuang Road,
Taichung, Taiwan
g
Department of Chemistry, Smt. Devkiba Mohansinhji Chauhan College of Commerce and Science, University of Mumbai, Silvassa, Dadra and Nagar Haveli (UT), 396
230 India

A R T I C L E I N F O A B S T R A C T

Keywords: Nanomaterials (NMs) have piqued the attention of scientists and researchers across many biomedical sciences
PAHs due to their superior physical, chemical, and magnetic properties. The efficacy and efficiency of NMs depend on
Nanomaterials adapting to specific site conditions and soil composition. NMs have lately received much attention in the context
Bioremediation
of polycyclic aromatic hydrocarbons (PAHs) polluted soil remediation and water mitigation because of their
Metal oxides
Semiconductor photocatalysis
unique properties resulting from their nanoscale sizes. The remediation of hazardous PAHs in water and soil is a
hot research subject. Because the exposure of PAHs in water and soil results in pollution, which raises major
human health concerns. The current review reports novel advancements in NMs that subsidize enhancement for
degradation of PAHs. Challenges to the fabrication of high activity-based photocatalytic materials are also dis­
cussed. Furthermore, this review delivers exclusive and wide-ranging perspectives on the fabrication of
nanomaterial-based photocatalytic systems. The knowledge of both soil remediation and water mitigation is also
updated.

1. Introduction rods, wires, tubes, and spheres. Therefore, NPs are of massive enthu­
siasm for scientists from diverse domains, including electronic, mag­
Nano-world research has attained a prime concern of the scientist netic, optoelectronics, advanced materials, cosmetics, pharmaceuticals,
community over the last decade. At the nanoscale (1 nm= 10–9 m), biomedicine, energy, catalysts, and environmental monitoring and
studies vary from the basic sciences (biology, chemistry, and physics) to detection [2, 3]. Biotic pollutants are harmful living substances that take
the more applied ones (electronics and materials). In the discipline of a long time to break down in the environment under natural conditions.
nanotechnology, one of the major advancements in the fabrication of Therefore, pollutant has sparked concern for their long-term persistence,
nanomaterial (NM) and their practical environmental applications [1]. bio-magnification, and bio-accumulation in ecosystems. Out of the most
Nanoparticles (NPs) are particles smaller than 100 nanometers in widespread toxic chemical compounds, the existence and addition of
diameter, comprise 20–15,000 atoms, and exist both on Newtonian and polycyclic aromatic hydrocarbons (PAHs) have received a noteworthy
quantum scales. They may be formed from various shapes, comprising fear over the past decades. PAHs own high semi-volatile and lipophilic

Abbreviations: PAHs, polycyclic aromatic hydrocarbons; NMs, nanomaterials; NPs, nanoparticles; Nm, nanometer; HMW, high-molecular-weight; LMW, light
molecular weight; PHE, phenanthrene; FLUO, fluorene; ANT, anthracene; NAP, naphthalene; EPA, environmental protection agency; UV, ultra-violet; MWCNTs,
multi-walled carbon nanotubes; CSIA, Compound-specificisotope analysis; FLAN, Fluoranthene; SWCNTs, Single-walled carbon nanotubes; CNTs, Carbon nanotubes;
G, Graphene; GO, Graphene oxide; rGO, Reduced graphene oxide.
* Corresponding authors.
E-mail addresses: [email protected] (A. Nizam), [email protected] (S. Ghotekar).

https://doi.org/10.1016/j.ceja.2022.100353

Available online 26 June 2022

2666-8211/© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
V. Dutta et al. Chemical Engineering Journal Advances 11 (2022) 100353

characteristics. These characteristics collectively lead towards a flocculation and adsorption, have the drawback of taking much time and
powerful attraction to be immersed and captured by biotic matter and merely converting PAHs into other poisonous byproducts [13]. PAHs, as
minerals in the soil, tailed by less accessibility for degrading agents and well as acknowledged as polynuclear aromatic hydrocarbons or simply
other microorganisms in the soil. poly-aromatics, are a class of over a ton of chemical molecules that are
Consequently, PAHs are prone to aggregate and hold as one of the hazardous and persistent in the environment. Hydrogen and carbon are
primary sinks in-ground soils [4]. PAHs are released and contaminate mostly assembled in two or more constant benzene rings. Their coupled
the environment as so many sectors are involved in producing gas, hy­ pi(π)-electron systems, which rely on the number of aromatic rings and
drocarbons, and coke, and processing industries of metal and wood. molecular weight, determine their physical and chemical characteris­
Other than human activities (e.g. biomass burning, industrial discharge, tics. PAHs are natural compounds that include at least 2 aromatic fused
petrol, tobacco smoking, cooking, gas, coal, waste incineration, and benzene rings organized in clusters or a linear form. PAHs are divided
wood combustion), in nature, they are produced by expected forest fires, into two classes based on their molecular weight: high-molecular-weight
natural oil seeps, responses in living beings and volcanic eruptions [5]. (HMW) and light molecular weight (LMW) [14]. If its structure is
PAHs are known for their carcinogenic nature, and their tenacity with entirely made up of benzene rings, or if 4, 5, or 6-member non-aromatic
toxicity increases with proliferation in its molecular mass. Oil leaking in rings are present, PAHs can also be characterized as alternant or
the water has recently gained attention owing to the deaths of many non-alternant. The low-molecular-weight PAH group possesses 2 to 3
aquatic animals and birds. Over 80,000 tonnes of PAHs are estimated to ring PAHs which include phenanthrene (PHE), fluorene (FLUO),
be unconstrained in water bodies each year [6]. The natural global anthracene (ANT), and naphthalene (NAP), whereas the
transmission of PAHs is represented in Fig. 1a. Due to bio-magnification high-molecular-weight PAH group possess a 4 to 7 ring system. Due to
in tropical species, PAHs are transmitted to humans via food consump­ their carcinogenic nature and teratogenic and mutagenic prospects, the
tion. According to several studies, PAH ingestion through regime (foods, US Environmental Protection Agency (EPA) named 16 PAHs a conceding
crops, and vegetables) is substantially more advanced than through gulp pollutant [15]. PAHs have a high persistency and biodegradability
of air [5, 7]. As a result, it is necessary to eliminate PAHs, and their considering the characteristics mentioned above.
metabolites, employing effective and innovative approaches. The past The half-life duration of PAHs, which is near 6–7 years for LMV and
decade of research engagement represents attention to photocatalytic 9–10 years for HMW, is being used to evaluate its carcinogenic persis­
NPs for remediation of toxic PAHs and green management. Most of the tence. PAHs show less biodegradability because they remain attached in
researchers focus on carbon NPs and their remediation. A survey found a strong bond with soil organic matter, making its mitigation much more
on the “Google scholar” by keywords “Photocatalytic for remediation of complex [16]. Many remediation technologies have been studied in this
toxic PAHs and green management” shows nearly 4290 published re­ respect, either on their own or combined with chemical, physical,
ports from 2011 to 2021 (Fig. 1b). thermal, and biological processes. Unfortunately, these approaches need
Nanomaterials with unique characteristics such as large surface area enduring management and intensive care, which fell petite of the
and semiconducting nature are an effective and promising technology end-point cleaning targets set out by new legislation and stringent
for removing environmental pollutants via adsorption and photo­ criteria. Using NMs to eliminate PAHs would be faster and more efficient
catalysis [8–12]. On the other hand, traditional physicochemical tech­ in this application. Throughout most cases, the excellent volume to
niques for removing hazardous pollutants, such as microbial surface area ratio of NMs aims to minimize the scope of soil redress

Fig. 1. (a) PAH production causes and foremost pollution pathways, (b) Survey based on the “Google scholar” by keywords, “Photocatalytic for remediation of toxic
PAHs and green management,” shows nearly 4290 published reports from 2011 to 2021.

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V. Dutta et al. Chemical Engineering Journal Advances 11 (2022) 100353

equipment, leading to waste formation and lower energy consumption typical breakdown approach that happens naturally in water settings,
[17]. After integrating NMs, the process will enhance PAH degradation several intermediate chemicals may threaten aquatic life. Anthraqui­
due to their inclusion of unique characteristics. Due to the uniformity none, for example, is produced by the photolysis of PAH.
and simplicity of chemical conditions and the relative ease of operation, Furthermore, direct photolysis is less efficient than alternative
scientists have typically concentrated on aqueous phases in incorpo­ methods in which light is paired with an oxidizing agent such as H2O2 or
rating NMs into remediation techniques [18]. Apart from aqueous ozone, in which heterogeneous and homogeneous catalysis is used, or
phases, soil, as a porous medium, may also be the giant sink for UV is even connected to typical ecological systems [21]. Photocatalysis
absorbing pollution, justifying the necessity of nanomaterials research has recently been developed as an advanced oxidation technique (AOPs)
to address the developing issues of PAH accumulation in soil. for the oxidation or mineralization of organic pollutants. It is a prom­
So far, no review of currently utilized nanomaterials for PAHs ising technology with high efficiency, minimum secondary pollution,
contaminated soil remediation has been presented. As a result, the simplicity of operation, and inexpensive treatment cost. According to a
current article provides an overview of various nanomaterials that have recent study, photocatalytic NMs are fabricated to remove contaminants
been employed for their effectiveness. Finally, opportunities for the from the environment [22]. Metal oxides (Cu2O, ZnO, TiO2, V2O5),
improvement in high-efficiency nanomaterials-based remediation tech­ metal selenides (such as CdSe, MoSe2), metal sulphides (such as Bi2S3,
nologies are highlighted. MoS2), and metal phosphides (such as Bi2S3, MoS2) have all been pro­
duced as semiconductor photocatalytic nanomaterials. (such as Co2P,
2. PAH degradation and its effects on environment Ni2P), multi-component oxides (such as Bi2WO6 and Bi2O2CO3) [23].
Fig. 2 illustrates the elementary mechanism of photocatalytic destruc­
PAHs have been treated using diverse techniques, including isola­ tion of contaminants using heterogeneous semiconductor photo­
tion, biodegradation, and thermal desorption. These methods have catalysis. In general, photon energy absorption equal to or more than the
drawbacks, such as the fact that pollutant is not a perpetual solution, energy gap needed by a semiconductor photocatalyst to produce e-/h+
thermal desorption is expensive, and microbial degradation of high couples activates the process, followed by reactive species generation
molecular weight PAHs (more than 3-rings). Also, it is deliberate due to (OH•, O•−2 ) redox reaction [24].
their high stability requiring the definite maintenance of optimum The optimal NMs for soil sanitization rely on the remedy technique
temperature [19]. Therefore, PAHs have been eliminated from water employed, the form of PAHs involved, the depth of treatment, the price,
using traditional chemical oxidation approaches. Several articles based and the soil parameters, rendering it a tough decision. However, con­
on the usage of traditional oxidants such as chlorine, potassium per­ structing practical guidelines would theoretically enhance the potential
manganate, and ozone have been reported. However, issues might to achieve and predict targeted deprivation outcomes. Consequently,
emerge during the decontamination phase. For illustration, disinfection this part is dedicated to studying reports that focus on the direct use of
by-products, including tri-halomethanes and haloacetic acids, have nanomaterial while considering all of the conditions cited above. The
responded with natural organic matter in water to generate carcinogenic NMs were categorized into nanoscale metal oxides, semiconductor
hydrocarbons like haloacetic acids and tri-halomethanes [20]. Ozona­ photocatalysts carbon, and polymer-based NM [25–31]. Effective NMs
tion and direct photolysis are most exploited to eliminate PAH among used for PAH degradation are listed in Table 1.
these conventional chemical approaches. Generally, PAH degradation
happens via two mechanisms: a) direct oxidation of the target compo­
nent by ozone and b) indirect oxidation of the target molecule by ●OH 2.1. Persistence and toxicity of PAH
from ozone transformation at alkaline pH. A significant restriction of the
ozonation process, aside from being impacted by the presence of ●OH Due to industrialization and anthropogenetic activities, PAH is the
scavengers, is the production of possibly hazardous by-products. One of most prevalent organic pollutant globally. These pollutants have com­
them is bromate, produced by bromide-containing fluids and is thought plex structuring containing multiple fused hydrocarbon aromatic rings
to be a human cancer-causing agent. Also, the non-economic cost of [39]. Natural emission of PAH occurs during a volcanic eruption,
apparatus and their maintenance and the power required to generate the vegetative decay, and forest fire, but the amount released is negligible.
activity are drawbacks of this technique. Although direct photolysis is a Major PAH emissions are from steel, Iron pesticides, fungicides, power,
cement, and aluminum industries. PAH is also emitted by diesel and

Fig. 2. The basic mechanism for photocatalytic degradation by using a photocatalytic semiconductor (Reprinted [24] copyright 2004 Elsevier).

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Table 1
Various photocatalytic systems for the degradation of PAHs.
Photocatalytic System Targeted Pollutant Metal oxides’ Contribution Results Reference

g-C3N4/Fe3O4 as visible-light Garden soil spiked The light absorption of g-C3N4 was prolonged to the The PHE photodegradation by g-C3N4/Fe3O4 [32]
semiconductor photocatalyst with 200 mg kg− 1 PHE visible region by loading Fe3O4. The electron-hole was 92% after 120 min
joining was halted in g-C3N4/Fe3O4
Cu2O/polylactic acid composite 0.2 g of soil sample Due to exceptional adhesion and grafting, the as- 67% FLU after 8 h of visible light irradiation [33]
under visible light spiked with FLU prepared Cu2O NPs disseminated consistently in was degraded
polylactic acid fibers, which significantly increased
the irregularity and surface area of the composite
Multiwalled carbon nanotubes Sandy loam and silt The results exhibited that MWCNTs impacted the At 2 mg g − 1 MWCNTs concentration, PAHs’ [34]
(MWCNTs) for sorption loam, both spiked with fate of PAHs mostly through hydrophobic sorption affinities did not affect
a single PAH interactions
Photocatalytic performance of Spiked with ANT, PHE, The nanocomposite was explored by high surface Photocatalytic degradation of ANT, PHE, and [35]
TiO2 based zinc and FLU; each 10 mg area (118.15 m2 g − 1) and negative charge (− 48.2 FLUO in the soil resulted in 86, 84, and 82%
hexacyanoferrate framework kg− 1 mV) at neutral pH, and narrow bandgap energy efficiency after 24 h sunlight irradiation
under sunlight (1.65 eV). The cation-π complexes were formed due
to interaction between PAHs and the
nanocomposite’s positive surface
Nanosize TiO2 under sunlight Alluvial soil and red Micro-nano size TiO2 performed rapid The reaction lasted for 5 h at a 5% (w/w) [36]
soil spiked with 100 photocatalytic degradation micro-nano size TiO2
mg kg− 1 PYR and aged
for 60 days
Photocatalytic effect of Fe2O3 Soil jagged with 16 PAH photodegradation by Fe2O3 was more favored Significantly higher photodegradation for BaP [37]
under homogeneous visible PAHs by HMW including FLUO, PHE, and BaP. The was observed (71%) in the presence of Fe2O3
light presence of Fe2O3 impeded the volatilization of compared to only 50% photodegradation in the
LMW PAHs by shielding the light from reaching the absence of Fe2O3.
PAHs, thus preventing its photolysis
Fe dopant influence on TiO2 Soil spiked from 0 to The photoactivity of TiO2 was enhanced by 83% PHE was removed after 2 h of visible [38]
performance under visible 100 mg kg− 1 PHE increasing the amount of Fe dopant irradiation at alkaline conditions.
light

gasoline-driven engines. Some physicochemical characteristics, such as and invertebrate organisms. The toxic effect on invertebrates (molluscs,
higher thermal stability, and hydrophobicity, are challenging to dete­ crustaceans) is reported to be high as they lack an effect on PAH
riorate PAH [40]. Studies have reported that the seasonal variation of metabolism, while its effect on vertebrates is more negligible as they
PAH, predominantly present in winter compared to autumn or summer, have a well-developed mechanism for metabolizing toxic lipophilic PAH
is mainly attributed to partial combustion of petroleum, poor photo to water-soluble, polar by-products that are readily excreted [45].
catalytical degradation, and high residential heating [15, 41]. PAH is Phenanthrene is one of the abundant PAH present in crude oil. Its
toxic to all life forms due to its mutagenic, carcinogenic, and teratogenic adverse effect on scallop Pecten Maximus was studied. It had a detri­
properties. This emphasizes the need for remediation performed by mental effect on its immune function and induced oxidative stress. PAH
physical and chemical methods. Biological means of bioremediation are is conducted by hemolymph, due to which hemocytes lose their mem­
mediated by a broad spectrum of microbes such as algae, fungi, bacteria, brane stability, and their number is reduced drastically, thus affecting
and enzyme-mediated processes. Humans are in constant contact with the immune function. PAH exposure showed lipid peroxidation due to
PAH as they are omnipresent in the air, terrestrial, and aquatic envi­ this oxidative stress and cell membrane integrity [46]. Similar kinds of
ronments. PAH are hydrophobic and lipid-soluble and tend to interact LPO were observed in sea bass Dicentrachus labrax. bivalves,
with the bilipid membrane of cells and enzymes associated with the M. galloprovincialis, and Mya arenaria [47–49]. Benz [a] anthracene
membrane and gets deposited in fat tissues [42]. (BaA) adversely affected bone metabolism when injected intraperito­
neally into nibbler fish. Malformation of the spinal was monitored with
suppressed expression of markers such as MMP9 and COL1A1 [50]. PAH
2.2. Toxicity of PAH on aquatic animals has a significant ill effect on the functioning of the vital organ liver.
Studies confirm that its effect is more on bottom-feeding, continuously
Four different PAH sources in the aquatic ecosystem can be broadly exposed to PAH in sediments. The biotoxicity assay performed for the
categorized as petrogenic derived from petroleum products. Over the Solea solea fish model indicated that PAHs were carcinogenic when
past few decades, we have heard about accidental oil spillage in oceans. tested with hepatocytes and liver tissue biopsy. When Bap, when
These crude oils with PAH are a significant component that tends to introduced intraperitoneally at a concentration of 10 ng/g body mass to
spread to larger areas and negatively effect on aquatic flora and fauna nibbler fish and Girella punctate. Both the fishes showed a similar
that persist for longer. His-happens to be the major source. Pyrogenic response when there was low liver metabolism. This has resulted in
source of PAH to water system if from incomplete combustion of fuels. malfunctioning of the endoplasmic reticulum and poor total cholesterol
PAH in the air phase follows a diffusive influx into water driven by the [51, 52]. Low molecular weight PAH is more water-soluble when
equilibrium between the air-water phases [43]. The biogenic source of compared to high molecular weight PAH. Due to this, they are readily
PAH is mediated by biological agents such as bacteria, algae, and plants, absorbed by the surface tissue and gills. PHA accumulation is core in
an organic metabolism to PAH. In contrast, the diagenetic source is the marine fish compared to freshwater fishes [53].
transformation of organic matter in the sediment. A major contributor to
environmental pollution is petrogenic and pyrogenic sources. The toxic
effect of PAH is manifested due to its carcinogenic and genomic toxicity. 2.3. Effects of PAH on human health
PAH at low concentrations is too toxic to a teleost fish embryo that
can affect its development in the early stages of development, leading to Human interaction with PAH exists in the environment through
hyper dorzalization, due to which the embryo fails to hatch. Cardiotoxic inhalation, ingestion and dermal contact. International Agency for
PAH affects normal heart development resulting in cardiac edema and Research on Cancer had classified PAHs as a potent carcinogen to
altering the heart rate [44]. PAH has a differential effect on vertebrate humans, falling under group1, 2A and 2B The first step in PAH

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metabolism is epoxidation mediated by the oxidase system to form PAH contaminated soil, water, and air. These processes are commercially
epoxides. In order to detoxify its adverse effects, they readily combine viable detoxification technology. The development of catalysts or
with glutathione, while unfused epoxides further break down into diols modification of the catalyst is one of the processes for photocatalysis.
and phenol. These metabolites are not adequately polar to be evacuated, TiO2 catalyst activated by solar photons, which involves electron-hole
and being highly reactive, they bind to DNA and cellular protein pair generation initiated by bandgap excitation, aids in the environ­
resulting in mutations and cancer. Long-term occupational exposure to mental detoxification by completely removing of pollutants in water,
PAHs has proven to cause liver, gall bladder, skin and gastrointestinal air, and soil. At times, the oxidation and reduction technologies are
cancers [54]. The teratogenic effect of PAH was examined with exper­ efficient approaches to execute the destruction of the contaminants,
imental animal mice. Data obtained indicates PAH as an embryotoxic particularly at low concentrations. The photogenerated holes respond to
substance that has resulted in low birth weight and congenital disabil­ the adsorbed hydroxyl groups and water to form hydroxyl radicals. The
ities. In human studies, exposure to PAH during pregnancy has resulted dissolved oxygen or other absorbed electron-acceptors (metal ions)
in malformation of the heart, low birth weight, and premature delivery. entrap photogenerated electrons. These toxic ions are removed in the
Cord blood samples, when examined, reported significant DNA damage latter case. Based on the above theory, waste streams containing organic
caused by PAH [55]. PAH can also affect the immunity in mammals. species and metal ions can be detoxified, making photocatalysis a green
PAH can cause immune suppression and high susceptibility to infectious management technology [64].
diseases and cancer. PAH can induce macrophages to produce higher Some photocatalysts reported in the literature for PAHs remediation
amounts of cytokines resulting in inflammation. PAHs can also destroy are mentioned below. Himanshu Gupta et al. [21] (2015) stated the
pre-B and T cells. It interferes in the myeloid haematopoiesis’s myeloid synthesis of pure iron oxides. They studied the photodegradation of
lineage and causes lymphoid tissue apoptosis [56, 57]. benzo[a]pyrene (B[a]P) in soils with varying pH levels in the presence of
goethite. The photodegradation of B[a]P followed first-order kinetics.
3. Photocatalysis as a physical process in remediation The results showed goethite form of iron oxide showed the fastest
Photocatalytic activity under short wavelength UV light. Photo­
Large amounts of pollutants are released into the environment due to degradation of B[a]P occurred through the oxidation metabolism [65].
increasing industrialization, and the disposal of industrial wastes has In neutral, acid, and alkaline soils, rate constants were 1.11 × 10− 2,
had significant environmental implications. Increasing the concentra­ 7.69 × 10− 3, and 9.97 × 10− 3 h − 1. These indicated that iron oxide and
tion of toxic ionic pollutants has led to persistence and bioaccumulation. the repair of benzo[a] pyrene-contaminated soil surfaces, oxalic acid is
Removal of toxic contaminants is achieved by various physical methods an excellent photocatalyst. Gupta et al. [23] (2016) developed nanorods
using physiochemical methods of metals such as electrokinetic methods, of akaganeite for photodegradation of PAHs in soil. Degradation studies
granular activated carbon, membrane filtration, photocatalysis, and revealed that phenanthrene decay was fastest under acidic conditions,
solid washing. The chemical process includes floatation, ion exchange, and 4 wt% akaganeite is present: it is at its best. Different degradation
coagulation, chemical precipitation, and flocculation. Bioremediation rates increased with the enhanced dose of oxalic acid due to the
involves the exploitation of microbes or their enzymes to purify the photo-Fenton-like process. Photodegradation of phenanthrene involved
polluted environment [58]. Among other organic pollutants, PAHs benzoic acid and its derivatives as the intermediate products. LC-MS
establish a class of dangerous biotic chemicals comprising two or more studies showed the disappearance of phenanthrene after 96 h on soils
bonded aromatic rings in angular, linear, and cluster arrangements. of different pH [21]. Marques et al. [63] (2016) evaluated the photo­
They have semi-volatile and high lipophilic properties, leading to a degradation of PAHs in two different Mediterranean soils,
durable affinity towards soil organic matter and minerals, making them coarse-textured and fine-textured soil. Experimental Studies indicated
less available to microorganisms or degrading agents. They are catego­ photodegradation depended on exposure time, the molecular weight of
rized into high and low molecular weight groups (HMW and LMW) [59]. each hydrocarbon, and soil texture. PAHs were photo-degraded more in
LMW contains 2 to 3-rings PAHs such as fluorine (FLUO), naphthalene fine-textured soil than in coarse-textured soil, and the former was able to
(NAP), anthracene (ANT), and phenanthrene (PHE), whereas HMW enhance sorption. Volatilization and sorption influenced PAHs of low
possesses PAHs containing four to seven rings [60]. The potency of molecular weight. On the other hand, medium and high molecular
numerous remediation skills has been explored with chemical, physical, weight PAHs undergoes photo-degradation of different ratios. The
thermal, and biological processes [61]. However, these methods require evolution of 16 PAH concentrations indicated faster detoxification in
long-term monitoring and control [59]. NMs have led to effective and fine-textured regosol soil over time. Nevertheless, after 28 days of in­
faster removal of PAHs [17]. The excellent surface-area-to-volume ratios cubation, the soil samples completely detoxified, revealing that
in NMs subsidize reducing soil remediation size, leading to low energy biodegradation and sorption are other mechanisms that have essential
consumption and waste generation [62]. To discourse the rising issues roles in PAH degradation in soil other than photodegradation. The
concerning the accretion of PAHs in soil, employing nanomaterials in strong isotopic effect observed in benzo(a)pyrene indicated
remediation techniques is the main focus of the ongoing research stage. compound-specific isotope analysis (CSIA) as a valuable tool to monitor
The photocatalysis technique employs light and semiconductors for in situ degradation of PAHs [23]. TiO2-graphene composites (P25-GR)
carrying out oxidation and reduction reactions. It displays non-toxicity, designed by Bai et al. [66] (2016) were fabricated via the hydrothermal
high stability, and no cause of secondary pollution. The characteristics treatment of graphene oxide (GO) and P25. The removal of PAHs was
of an ideal Photocatalyst are narrow bandgap energy, enhanced charge investigated at an optimal graphene ratio. Phenanthrene (PHE), benzo
separation, lower recombination rate, low cost, good stability, and [a]pyrene (BaP), and fluoranthene (FLAN) were selected as models of
higher visible-light efficiency. The photocatalysis mechanism involves PAHs. From experimental results, it was concluded that P25–2.5% GR
the generation of hydroxyl radical and superoxide anion. Both species improved both adsorption and photodegradation. After two hours of
act as an oxidant necessary to degrade organic compounds. Carbon-di- photocatalysis, 80% of PAHs were removed. Aromatic intermediates
oxide and water are the less harmful reaction products obtained after indicated reaction pathways involving the formation of free radicals,
mineralizing the organic pollutant. Soil depth plays a pivotal part in the leading to the degradation of PAHs [66]. Himanshu Gupta et al. [5]
photodegradation of PAHs. More, the soil depth enhances the confron­ (2017) demonstrated a cost-effective protocol for iron oxide preparation
tation of PAHs to be photodegraded. Other factors that affect photo­ without any capping agent. Goethite (α-FeOOH) and magnetite (Fe3O4)
degradation are temperature, soil particle size, humic acid under UV-B were two different iron oxide nanoparticles synthesized and used to
radiation, soil type, soil layer thickness, and light absorption spectrum of degrade anthracene under UV light. Both the forms of iron oxide NPs
each PAH in soil [63]. Heterogeneous photocatalysis is a green tech­ showed good photodegradation activity and followed first-order ki­
nology for removing inorganic and organic compounds from netics. The half-lives of anthracene degradation revealed that the

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photocatalytic capacity of magnetite is low as compared to goethite may Doping caused an increase in surface area with a decrease in photo­
be attributed to the small bandgap of magnetite leading to electron-hole luminescence intensity and bandgap energy. PC and TOC results
recombination. Xiaolong Yang et al. [67] (2018) designed graphene revealed the superior interaction of H2O or O2 with charge carriers to
oxide enwrapped silver phosphate as a photocatalyst employed under produce hydroxyl radicals which eventually mineralized the PAHs under
visible light irradiation for the photocatalytic degradation of PAHs (such sunlight. Nanocomposite degraded the PAHs by attacking hydroxyl
as naphthalene, phenanthrene, and pyrene). Three wt% of the synthe­ radical on the less hindered site via oxidative degradation into smaller
sized photocatalyst exhibited the highest performance of the photo­ and safer by-products such as (Z)‑prop-1-ene-1,2,3-triol and (E)−
catalytic degradation of phenanthrene under visible light and complete 3-hydroxyacrylaldehyde [35]. Wang et al. (2019) confirmed from the
removal in 7 min with 1 g/L photocatalysts. With the increasing number studies conducted apart from hydroxyl radical and ESR analysis that
of aromatic rings in the reactant, the degradation rate also increased, superoxide anion is the main species accountable for PHE degradation.
and the rate constant (k) followed the order pyrene>phenan­ They developed an approach to synthesize g-C3N4 /Fe3O4 under solar
threne>naphthalene. Superoxide radicals and holes played a primary light irradiation accountable for generating active radicals, including
role in the photodegradation process of naphthalene and phenanthrene superoxide anion and hydroxyl radical. The reaction between oxygen
and OH radicals in the photodegradation process of pyrene [68]. and excited electrons is responsible for forming a superoxide anion for
Theerakarunwong et al. (2018) designed Fe doped TiO2 nanocatalyst photo-degradation [32]. Qin Xu et al. in 2020 prepared Cu2O/PLA
(Fig. 3) using modified sol-gel and impregnation approaches toward nanofibres by surface modification via the EB irradiation approach. FTIR
photodegradation of PAHs such as anthracene, phenanthrene, and flu­ spectrums attributed to strong hydrogen bonding between Cu2O NPs
oranthene, contaminated soil under visible irradiation. The results and PLA fibers, excellent adhesion, and grafting enhanced the roughness
evinced that the effect of visible irradiation using Fe-doped TiO2 showed and surface area of the nanocomposite. These bifunctional nanofibres
the fastest photodegradation activity than the undoped TiO2 due to the exhibited excellent photocatalytic performances, effective for the
high surface area of Fe-doped TiO2. GC–MS studies revealed that PAHs’ degradation of various organic pollutants in soil and water systems (such
photoactivity involves ring-opening, hydroxylation, and rearrangement as fluoranthene and MO). The Cu2O/PLA nanofibres obtained by various
reactions. Heptadecane, octadecane, cyclohexane, 9-octadecanoic acid EB irradiation doses showed other photodegradation efficiencies of
and 15-hydroxypentadecanoic acid were found to be the main in­ fluoranthene in soil. These nanofibres showed the highest activity at 12
termediates of PAH degradation. The photocatalytic process under kGy. The free radicals also increased accordingly by increasing the EB
visible light is a highly efficient and low cost to mitigate the toxicity of irradiation dose from 2 to 12 kGy, which promoted the continuous
these PAHs in complex soil samples [69]. Rachna et al. (2019) prepared formation of hydrogen bonds and grafting reaction. However, under a
titanium dioxide-based zinc hexacyanoferrate framework higher EB irradiation dose (50kGy), excessive free radicals would hinder
(TiO2@ZnHCF) nanocomposite via A. indica mediated co-precipitation the graft reactions between Cu2O and PLA and disrupt hydrogen bonds
approach. Fall in the concentration of PAHs (soil-82–86% and river already formed, thus affecting the grafting ratio and effective removal of
sediment- 81.63–85.43%) under sunlight. With time higher photo­ fluoranthene (FLU). And 67% of FLU degraded after eight hours under
degradation performance of the nanocomposite was exhibited than the visible light irradiation [33].
bared one. Diffusion caused by the interaction between the organic
content of soil/ PAHs attributed to the slow degradation of PAHs in soil.

Fig. 3. (a) Photocatalysis mechanism for degradation of PAHs, (b) Photocatalytic degradation of PAHs using TiO2 semiconductor photocatalyst (Reprinted [69]
copyright 2017 Elsevier).

6
V. Dutta et al. Chemical Engineering Journal Advances 11 (2022) 100353

3.1. Carbon-based nanomaterial in PAH remediation Chen and co-workers [74]. They have considered graphene (G), gra­
phene oxide (GO) and reduced graphene oxide (rGO) for the adsorption
Carbon and carbon-based NMs are novel materials (Table 2) due to of diverse aromatic compounds. The adsorption capacity of the hydro­
their properties and applicability. They have widespread potential in philic GO was the lowest. The recovery of hydrophobic-conjugation
various applied chemistry fields. A recent trend is using the class carbon atoms as active sites dramatically boosted RGO and G adsorp­
mentioned above of materials in PAHs remediation. A large group of tion [73, 75]. The two-dimensional (2D) planar graphene sheets are
PAHs are a threat to the environment. There are different reports of inefficient for practical applications. Despite the big disadvantage, ma­
remediation of these compounds, either through adsorption or degra­ terials modified can be used for the same purposes. Different reports
dation, found in the literature. Numerous carbon nanomaterials, demonstrate the assembly of 2D graphene-based materials into three
including fullerenes, single-walled carbon nanotubes (SWCNTs), multi- dimensional (3D) porous structures to improve their adsorption capac­
walled carbon nanotubes (MWCNTs), and graphitic materials, have ity. PAH removal from a water-based matrix using reduced graphene
extensively been used in the process of remediation [70]. Among the oxide was demonstrated by Huang et al. (2018) [76, 77]. Using 2-ethyl­
materials researched, carbon nanotubes (CNTs) are of high interest due hexyl acrylate and ethylene glycol dimethacrylate as monomer and
to their notable features such as higher chemical stability, thermal crosslinker, RGO/polyHIPEs with open-cell structures were effectively
resistance, adsorption capacity, and pH range stability. SWCNTs and produced, and the resulting RGO/polyHIPEs were employed as sorbents
MWCNTs are two of the most promising NMs for eliminating contami­ for PAH removal [78].
nants as adsorbents. The high surface-active site to volume ratio and
regulated pore size distribution of traditional adsorbents. Excellent π-π 3.2. Nanocomposites/engineered nanomaterial in PAH remediation
and van der Waals interaction of these materials with PAHs make them
sufficiently successful in the remediation. A concern in this regard is the Composites provide flexibility in altering properties and functional­
hydrophobic nature of CNTs, however, the high-water transporting ities. Nanocomposites and engineered materials have superior impor­
potency of water masks this disadvantage. Akinpelu et al. demonstrated tance in different applications. PAH remediation has been successfully
the remediation of phytotoxicity of sediments contaminated by phen­ carried out using such materials with added advantages in their physical
anthrene. The in-situ remediation of phenanthrene with MWCNTs and chemical properties. One challenge faced in any remediation is
reduced both aqueous concentrations of phenanthrene and the phyto­ removing the material used for the purpose after the completion. Diverse
toxicity of the sediment. However, one issue with the use of MWCNTs is methods have been introduced in order to remove these materials. One
the possibility of agglomeration, which is a setback for the remediation way that has potential in a practical aspect is making the adsorbent
process as well [71]. magnetic. This will allow the removal after the reaction with an external
Agglomeration can effectively reduce the surface area and surface- magnetic field source. Naphthalene and its derivatives adsorption on
active site to volume ratio. A solution to it is the introduction of func­ magnetic graphene composites reported by Yang et al. demonstrated the
tional groups. In the study by Akeem et al., the removal of naphthalene enhanced advantages over the previously discussed carbon material.
was effectively carried out using hydroxyl functionalized multiwall The electron-donor–acceptor (EDA) interaction was hypothesized as the
carbon nanotubes (MWCNTs-OH). In comparative study followed major mechanism for aromatic chemical adsorption, and the adsorption
demonstrated a high mesoporosity of MWCNTs-OH than MWCNTs. This performance enhanced as the dipole moment rose. Further investigation
was in correlation with the Langmuir model for naphthalene adsorption of the mechanism of action revealed that the adsorption approach is
on MWCNTs-OH. It was observed to be higher when compared to endothermic and spontaneous [82]. In a similar work carried out by
MWCNTs [72]. Graphene-based materials are also considered effective Mahpishanian et al. [83], the nanocomposite Fe3O4@SiO2@GO–PEA
in removing PAHs due to their high specific surface area and large π-π was used for magnetic solid-phase recovery of PAHs from water samples
electron system. The adsorption of PAH such as phenanthrene, naph­ after GO was covalently immobilized on silica-coated magnetite and
thalene, and pyrene using graphene (G) and graphene oxide (GO) are subsequently modified with phenylethylamine. The adsorbent’s unique
discussed in the studies conducted by J. Wang and co-workers [73]. Two structure allowed for a wide surface area and high adsorption [84]. The
different mechanisms of adsorption are discussed here. The first one is hydrophobic PEA groups on the adsorbent’s surface aid in the adsorp­
the π-π interaction of graphene to PAH due to the flat surface and the tion of PAHs through the stacking contacts, while the hydrophilic
sieving effect of groove regions formed by wrinkles on the graphene oxygen-containing functional groups on the GO surface aid in the ad­
surface. sorbent’s dispersion in aqueous matrices [83]. An interesting composite
In comparison with graphene, graphene oxide (GO) displayed less made from graphene is the graphene nanoplatelet supported MIL-101
affinity to the PAH attributable to limited π-π interaction and interaction composite material (GNP/MIL-101). The material was reported in the
limited to the edges where carboxyl groups are present. The efficiency of removal of naphthalene by adsorption. The extensive adsorption effi­
adsorption, therefore, drastically reduces from graphene-to-graphene ciency of 93% was closely connected to the extensive adsorption effi­
oxide. These results are in agreement with the study conducted by X. ciency. Moreover, a magnetic composite of carbon nanotube was used in
the remediation process of PAH.
Table 2
The magnetic adsorbent was fabricated by incorporating Fe3O4 NPs,
Carbon-based NMs and their properties. MWCNTs and polypyrrole. π–π stacking interactions play a major role
here due to the presence of CNTs and the aromatic polypyrrole π bonds.
Sl Carbon based nanomaterial Substrate Reference
No used
However, the same polypyrrole has the important function of material
dispersion in the aqueous solution due to its polar -NH2 groups. Due to
1 Multi-walled carbon Surface sediment contaminated [79, 80]
their versatile properties, different oxides of iron and carbon composites
nanotubes (MWCNTs) with Phenanthrene
2 Hydroxyl functionalized Naphthalene [81] are also a promising group of materials. To make the superparamagnetic
multiwall carbon nanotubes carbon/ZnFe2O4, ZnFe2O4 NPs were encased in a carbon (C) matrix. The
(MWCNT-OH) amputation of naphthalene and 2-naphthol from aquatic systems has
3 Graphene (G), graphene Naphthalene, pyrene, [77] been investigated using the C/ZnFe2O4 nanocomposite as an adsorbent.
oxide (GO), and reduced phenanthrene, fluoranthene,
graphene oxide (rGO) anthracene, benz[a]anthracene
The electrostatic interaction mechanism between PAHs and C/ZnFe2O4
etc. has been discussed for the sporty remediation of pollutants from the
4 Graphene (G), graphene Nitroaromatic compounds [74] aqueous phase [85].
oxide (GO), and reduced
graphene oxide (rGO)

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V. Dutta et al. Chemical Engineering Journal Advances 11 (2022) 100353

3.3. Inorganic nanomaterial in PAH remediation wherein the organic ligand (HS-β-CD) act as the capture agent of various
PAHs [97]. Conclusively, it can be stated that functionalized metal NPs
Adsorption is a means of remediation to remove toxic compounds prove to be more reliable compared to their pristine form (unfunction­
like PAH and metals from environmental sources. Nanoparticles (NPs), alized metal NPs) for the sensitive and selective detection of PAHs,
due to their exclusive characteristics like size and large surface area, which has the potential in developing a sensing device that can be uti­
have played a vital role in PAH remediation. Various organic and lized commercially for the onsite finding of PAHs in various environ­
inorganic NPs are at the forefront of this process. This section focuses on mental models [98].
using of iron, silver and gold-based nano-adsorbents for PAH remedia­
tion. Buragano et al. used unfunctionalized magnetite NPs to remove 4. Challenges and future perspectives
PAH (phenanthrene) from soil samples. Batch experiments were per­
formed to study the effect of NPs dose (0.5–2%) on adsorption of PAH. • Despite the many benefits of using NPs in PAH-contaminated water
Immobilization of PAH is attributed to the magnetic property of and soil bioremediation, some drawbacks exist. The most significant
magnetite NPs and 1% NPs dose outperformed the rest [86]. An inte­ issue of using NPs in soil has been their toxicity, which can be
grated approach of bioremediation and using Fe NPs prepared by the attributed to the following factors:
Fenton-like oxidation method has resulted in 100% biodegradation of Because NPs contain PAHs and heavy metals, they could act as a
naphthalene and 28.9% of phenanthrene. transporter of these compounds in the soil complex, causing sec­
Further to improve the efficiency for biodegradation of phenan­ ondary contamination after application.
threne. Fe NPs fabricated using tea extracts were employed, resulting in NPs can raise trace and nutritional metal levels, some of which
100% phenanthrene removal [87]. Fe3O4 NPs were used as a catalyst in may be hazardous to earthworms and other biological constituents in
PAH decontamination from the soil. 99.33% of pyrene was removed the soil and water.
when imperiled to sono-Fenton like oxidation. The optimum conditions Changing the pH of soil and water due to the addition of NPs could
for the experiment, 78.37 mM H2O2 concentration, Fe3O4 NPs dose of have hazardous consequences for soil-dwelling organisms.
18.17 mM, ultrasonic power of 313.2 W and pH 3.46 were employed • Due to the influence of dry material on animal systems, a high
[88]. In general, functionalized/non-functionalized gold and silver incidence of NPs causes physical harm to soil invertebrates.
nanoparticles are widely used to isolate PAHs as they exhibit a strong
affinity towards them which greatly helps in their isolation and pre­ As a result, a toxicological examination is required before and after
concentration from various sources like drinking water and soil, etc. treatment because bioremediation does not always reduce toxicity. In
These synthesized NPs performed better than Ag NPs prepared by the addition, high bioremediation (greater than 90%) does not always imply
wet chemical method in the bioremediation of phenanthrene, pyrene, that the PAH-contaminated soil and water are nontoxic. Designing
and anthracene [89]. Gold (Au) NPs functionalized with 3-mercaptopro­ appropriate production conditions and NP application rates could help
pyltrimethoxysilane and various other thiolating agents have been used reduce harmful effects in the soil.
to detect 16 PAHs with a detection limit ranging between 0.8 to 60 mg L
− 1
, a total recovery of 44.6–90.5% [90]. Seawater is a significant source
5. Conclusion
of PAHs since most industrial effluents are released into them, causing
severe environmental damage to aquatic flora and fauna. In order to
Over the last few decades, a detailed overview of PAH degradation
detect and quantify PAHs from various seawater samples, Ali et al.
employing NPs has been described. The magnetic, electrical, catalytic,
synthesized gold immobilized mesoporous magnetic silica NPs, which
and optical properties of NPs are impressive. As a result, the NPs might
exhibited a discovery limit of 0.002–0.004 μg L − 1 [91]. Most of the
be used to remediate the environment effectively. The potential of NPs
PAHs are not present individually in a sample but as a mixture which
was explained in terms of mechanisms and interactions as a biological
makes the in-situ identification challenging to carry out. Recently,
remediation technique for PAHs in water and soil. Because of their
surface-enhanced Raman scattering has been used as a secondary
exceptional physicochemical properties, NPs may effectively degrade
approach for many environmental examinations due to the local surface
PAHs in soil and water as a photocatalyst. Furthermore, the effects of
plasmon-induced electromagnetic enhancement. Analytes that are SERS
various parameters on PAH decomposition have been thoroughly
active exhibit an instinctive affinity towards the surface of noble metals
examined. As a result, in the coming years, NPs may be regarded a
wherein the electromagnetic fields are localized [92]. Jing et al. [93]
possible material for environmental remediation. This review provides a
established a novel substrate created on thiol functionalized core-shell
strong basis for the future development of NPs for the degradation of
magnetic NPs (Fe2O3@Ag) to detection of PAHs. The detection limit
PAHs.
obtained was 10− 5 to 10− 7 M (molar). Glycidyl methacrylate-ethylene
dimethacrylate was used by Wang et al. to functionalize Au NPs,
wherein the polymer acted as a hydrophobic layer which increased the Conflict of interest
affinity towards PAHs compared to pristine Au NPs. The SERS substrate
(GMA-EDMA@Au NPs) was employed to detect anthracene, phenan­ The authors declare that there are no conflicts of interest regarding
threne, and pyrene with a detection limit of 0.93 × 10− 7, 4.5 × 10− 7, the publication of this manuscript.
and 1.1 × 10− 7, respectively [94]. Later, Wang et al. used an Ag
NPs/graphene hybrid for the detection of phenanthrene, anthracene,
Funding information
and pyrene with a very high exposure limit of 0.73 ppb, 1.1 ppb, and
0.57 ppb, correspondingly. It turns out that the PAHs get immobilized on
Not available
graphene, which acts as an added advantage for the detection and
quantification of these analytes, thereby helping the design, develop­
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