A Concise Account of The Studies Conducted
A Concise Account of The Studies Conducted
A Concise Account of The Studies Conducted
Abstract
The growing use of engineered nanomaterials, courtesy of their exhibition of a plethora of desirable
properties, in technological, industrial and biomedical fields as well as their extensive use in several
consumer products warrants a range of insightful studies on their fate, transformation and all sorts
of adverse impacts following their final deposition in the eco-system. Furthermore, their detection in
waste leachate yet more heightens the concerns of the environmental risks these nano-sized materials
actually pose, triggering investigations seeking to determine their optimum concentrations for their
toxic effects on the biosphere. Besides, nanomaterials are capable of undergoing several transformations
both in the environment and within biological systems in the form of interactions with macromole-
cules, redox processes, bio-stimulated degradation of their surface coatings, aggregation and dissolu-
tion, which alter their fate, transport and implications. This discourse therefore seeks to discuss these
critical transformations with an aim to present fresh information and key aspects emerging from recent
investigations. The toxic effects of nanoparticle accumulation in terrestrial and aquatic organisms also
find room in the discourse. The profound alteration of the fate, transport and toxic implications induced
by transformation of nanoparticles to ions via their dissolution has been looked into. For instance, it is
worth assessing the potential implications and genotoxicity of the widely touted bactericidal Ag+ ions
that in several ways get released from used Ag nanoparticles into terrestrial, aquatic and atmospheric
environments. Worth-noting, in this regard, are the means of transport of Ag+ ions into the internal
system of higher organisms, including humans and mammals. Likewise, of particular relevance are the
ecotoxic effects of the bactericidal ZnO nanoparticles after their transfer into biota. Several studies have
zeroed in on the dissolution of Zn2+ ions, ROS (reactive oxygen species) generation and other photo-
induced mechanisms while seeking to expound on the inimical nature of ZnO nanoparticles. The dis-
course finally acknowledges the current paucity of knowledge and techniques required to ascertain the
properties of the nanomaterials under environmental conditions, which hinders definitive study of the
rates and extent of their transformations and thereby their ultimate fate, transport and the scale of their
negative implications. The discourse thus concludes with a stress on further research into some of the
key aspects of the behavior of nanomaterials in environmental conditions.
Chaudhery Mustansar Hussain (ed.) The ELSI Handbook of Nanotechnology: Risk, Safety, ELSI and Commercialization,
(51–66) © 2020 Scrivener Publishing LLC
51
52 The ELSI Handbook of Nanotechnology
3.1 Introduction
The field of nanoscience and nanotechnology has undergone massive expansion in the
recent past and engineered nanomaterials have been produced in vast quantities for use
in commercial, industrial and research sectors. Engineered nanomaterials are substances
with at least one dimension scaling within the range of 1–100 nm. Therefore, a natural
spike in their release into the environment has been a marked phenomenon in the past
few years. Concomitantly, investigations probing into the threats they pose began. In this
course, many aspects whose inspection was imperative for proper evaluation of risk came to
the fore. For instance, it was observed that transport of engineered nanomaterials in aquatic
medium was greatly influenced by sedimentation rate, which in turn was determined by the
presence of electrolytes, stabilizers or NOM, viscosity of the medium and the initial concen-
tration of the engineered nanomaterials [21, 22]. A retarded sedimentation is thus expected
to be associated with longer transport distances. Additionally, engineered nanomateri-
als might undergo sulfidation and interactions with humic substances (HS) and natural
organic matter (NOM) which can alter their behavior and final deposition [53–57]. Redox
processes [58–64] might also induce radical transformation of engineered nanomaterials.
So far as toxicity is concerned a lot of investigations have been modeled to understand
a wide range of parameters that can affect toxicity. There have also been studies made to
locate the possibility of genotoxicity associated with exposure to engineered nanomaterials
[103, 113]. Here, in this discourse, an earnest attempt has been made to provide a vantage
point that looks over a range of issues concerning the transport, fate, transformation and
toxicity of engineered nanomaterials.
tend to accumulate in a definite region of space in air. Such localized accumulation leads to
the greater concentration of engineered nanomaterials in the atmosphere which might facil-
itate their aerial alteration, both physical and chemical characteristics that in turn might dic-
tate their subsequent fate and transformation in the remaining segments of the biosphere [3].
There are major shortcomings in the measurement of the concentration of engineered
nanomaterials in air. One, the device is unable to distinguish engineered nanomateri-
als from background particles [4]. Two, aerosol mass spectrometer is unable to make a
measurement of metal and metal oxides [4]. Three, existing devices for measurement are
sensitive to size and are unresponsive towards density [5]. Four, current instrumentation
procedure cannot yield detection of trace amounts [6]. Five, some transition and heavy
metals are usually beyond detection [6]. Further research in this area is thus the only way
ahead in light of the aforementioned limitations concerning measurement and detection of
airborne engineered nanomaterials.
The difficulty accompanying the quantitative detection of engineered nanomaterials
when present in traces and small sizes and the very sophisticated nature of the system pre-
cludes a detailed inspection of their aggregation and deposition in air channels. Despite
this, one investigation [1] observed that for a span of ten days’ retention, one-thirty-sixth
of the admitted engineered nanomaterials eventually displayed a continued survival in the
lower layers of air, suggesting that much had undergone settlement. On the other hand,
another study [7] reported their long-term persistent presence in the lower atmospheric
level citing their agglomeration in sizes beneath 1 µm. Nevertheless, the transport of engi-
neered nanomaterials in atmosphere will be restricted by their low concentration, which is
an outcome of their low volatility and consequent fast settlement.
Engineered nanomaterials may also undergo sedimentation and in this course settle
down under the action of gravity either as aggregates or in their adsorbed state with natural
organic matter (NOM) or other particles. Greater aggregation resulting in bigger size leads
to higher sedimentation. Usually, a time lag separates aggregation from sedimentation, in
which cases sedimentation goes at a slower pace. Sometimes, however, initial aggregation
happens so fast that sedimentation takes place concomitantly. The sedimentation rate is
chiefly controlled by the size of aggregates. Other parameters that influence the pace of
sedimentation are the presence of electrolytes, stabilizers or NOM, viscosity of the medium
and the initial concentration of the engineered nanomaterials [20, 21]. The prerequisite for
the occurrence of sedimentation is the velocity of settling having greater magnitude than
the critical velocity of settling [22]. Sedimentation is found to proceed through three stages:
a slow initial stage followed by a rapid settling and finally another slow deposition due
to a lowered concentration of suspended engineered nanomaterials [20]. Sedimentation
rate is found to be affected by pH and concentration of NOM. A slower sedimentation
will prolong the presence of engineered nanomaterials in the medium and, so, they have
a greater chance to travel longer distances in water. As a rule, seawater happens to have
greater sedimentation rate than other forms of water bodies. It is worth mentioning here
that sedimentation rate varies across seawater, freshwater, groundwater, storm-water and
other kinds of water.
[28–32]. The size of aggregates exerts a great influence on the transport of engineered nano-
materials contrary to the minimal influence exerted by the size of the primal nanoparticles.
Greater particle or aggregate size associated with greater attachment efficiency implies less-
ened mobility of engineered nanomaterials [30, 31]. However, Wang et al. [33, 34] reported
a lowered mobility of small-sized SiO2 NPs attributable to the relative charges on the sur-
face. Size is found to influence the way particles interact with themselves and soil matter
apart from determining their physical and chemical [33, 34]. Surface charge, on the other
hand, strongly determines the interplay between particles themselves and between particles
and soil components [35, 36]. The pH of the soil wields great control on aggregation. With
a pH that facilitates the generation of zeta potential close to zero, repulsive interactions
between particles lessen, leading to increased aggregation and attachment to soil particles.
Soil characteristics, such as the size of soil particles and soil pores, tend to exercise great
control on transport of engineered nanomaterials in soil. Pore-size equal to or greater than
aggregate size slows down transport by straining [37, 38] and by filtration via removal of
the particles by interception, diffusion, and/or sedimentation [12, 27, 28, 39]. This leads
to the greater retention of aggregates in the upper layers of soil. Also, the flow velocity of
groundwater is known to have a great impact on the mobility of engineered nanomaterials
[32]. A minimum flow velocity associated with greater collision frequency is likely to hin-
der transport while a vigorous flow, partly owing to lowered attachment efficiency, favors
mobility [40, 41].
purging out by rain was also found to be dependent on particle size [45–47]. The size and
quantity of engineered nanomaterials in air will also be affected by atmospheric turbulence,
temperature and relative humidity [48]. Engineered nanomaterials, to an unknown extent,
may also undergo degradation via photolysis and oxidation while airborne [49].
containing phosphate by transformation into zinc phosphate [67]. While another study
reported adsorption of phosphate on ZnO surface to be the cause of the prevention of ZnO
dissolution [68]. Similar outcomes have also been reported in the case of Fe3O4 NPs at low
pH [69]. Ag exhibited lower affinity for phosphates [70]. TiO2 NPs were apparently ren-
dered more stable when environed by phosphate-rich water via an increase in their suspen-
sion abilities [71, 72].
Aggregation, as discussed in earlier section, is an inevitable phenomenon the engineered
nanomaterials are subjected to. Only coatings, fabricated or later acquired, may delay
aggregation. Among homoaggregation and heteroaggregation, the later plays a critical role
in modifying the behavior of engineered nanomaterials in the medium. For instance, a
heteroaggregation with clay may impart clay-like mobility to the engineered nanomaterial
[73]. Aggregation decreases surface area and as such truncates reactions associated with
large surface area like ROS generation. This lowers toxicity. Aggregation may further reduce
dissolution and degradation, leading to an enhanced persistence of engineered nanomate-
rials. Even bioavailability shrinks with aggregation since aggregation leads to bigger sizes
whose passage through cell wall stand hindered.
Biological transformation of the coating as well as the core of engineered nanomate-
rials may even occur. Such transformations bring about alterations in the stability and
behavior of engineered nanomaterials and as such affect their persistence, bioavailability
and toxic power [74–76]. Upon uptake by organisms, engineered nanomaterials inevitably
interact with biological molecules that more often than not bring about a variation of their
surface composition, structure, size, electrophoretic mobility, etc. Likewise, interactions
with geo-macromolecules like proteins, polysaccharides, HS and other NOMs may result
in grave changes in the properties, persistence and toxicity of engineered nanomaterials.
Heteroaggregation with NOMs leads to varying aggregation and dis-aggregation behavior.
Also, triggering of redox processes has been spotted, as discussed in the case of ceria in an
earlier section.
3.4 Toxicity
3.4.1 Toxicity in Aquatic Biomes
Investigations were carried out to evaluate the toxicity of nano-sized Ag, TiO2 and ZnO
through an assessment of the immobilization of Daphnia magna, a phytoplankton resid-
ing abundantly in freshwater. Ag was found to form huge and stable agglomerates and at
enhanced solubility was found to exert a high level of toxicity. Stable nano-scaled agglom-
erates of TiO2 in an ambience of low ionic strength demonstrated toxicity that heightened
with dissolution. But with high ionic strength, toxicity wasn’t detected. Similar observations
could be made with small and stable agglomerates of ZnO [77–79].
Using the strains Escherichia coli, a study showed toxicity of CuO, TiO2 and ZnO via
enhanced generation of ROS [80]. The study further stressed the higher toxic impacts of
nano-sized components than their bulk counterparts. Nano-sized Ag could cause annihila-
tion of bacterial DNA, simultaneously effecting a serious disruption of the cloning phenome-
non [81]. Furthermore, AgNPs could bring about impairment of the bacterial cell membrane,
leading to leakage of cytoplasm and thereby disintegration of bacterial cell [82, 83].
58 The ELSI Handbook of Nanotechnology
With algae, toxicity was found to depend on doses of engineered nanomaterials and was
mediated by ROS formation and creation of oxidative stress [84–86]. Engineered nanoma-
terials like nano-sized TiO2 [87], fullerenes [88] and single-walled carbon nanotubes [89]
induce biochemical transformations in the brain of fish that might manifest as behavioral
changes. Lipid metabolism also gets perturbed. However, either this disruption happens
too slowly to surface as a noticeable effect or an optimum accumulation is required for the
observation of an effect [90].
standard procedure to measure and detect engineered nanomaterials over a large spectrum
of concentration needs to be plugged soon. Also, concentrations that can match up to the
ones that prevail in a real environment have not been tested. This gap may impact our
comprehension about the various phenomena such as aggregation, dissolution, sedimen-
tation, adsorption, etc., that constitute the fate and transformation of engineered nano-
materials. The pace and degree of transformation are likely to vary across ions and other
complex organic substances present in the biosphere and so wide and extensive studies
in this regard must be made and data generated must be standardized for statistical com-
parison across sizes, shapes, kinds, properties and medium of engineered nanomaterials.
However, although toxicity at the current concentration of engineered nanomaterials may
be dismissed, chronic deposition and thereby chronic exposure may generate effects that
have not been looked into. Furthermore, toxicity to soil organisms has not been investi-
gated extensively and more work factoring in the sophisticated nature of the exposure of
soil organisms to engineered nanomaterials can be expected in this area. Also, little about
the extent of percolation of engineered nanomaterials to groundwater and their toxic effect
on the biomes therein are known.
3.6 Conclusion
Despite the shortcomings of the various procedures adopted for risk assessment of engi-
neered nanomaterials, a lot has been studied about their transport, fate, transformation and
toxicity in recent years. This discourse has thrown light on the various reports that have
thus emerged. It is worth mentioning here, that to have a comprehensive understanding of
the noxious effects of engineered nanomaterials on living organisms, it is imperative to gain
deeper insights into the processes preceding their arrival at the biological endpoint, namely
fate and transformation. For safeguarding mankind, restoration of the ecological balance is
currently a matter of growing priority in light of the relentless impairment the ecology has
undergone over the past many years.
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