Nanowires and Pollution

What is a Nanowire?
It is a nanostructure with the diameter of the order of a nanometer
(109 meters) which is extremely small.
There is no restriction on how wide they can grow, but cannot
grow more than a few nanometers in height.
Have nanometer size in one of the dimension which produces
quantum confinement in material and changes its properties.
These can be of following types:-

Metallic - Made from Nickel, Platinum or Gold

Semi-conducting - Comprises of Silicon, Indium phosphide or
Gallium Nitride

Insulating - Silicon Dioxide or Titanium dioxide

Molecular

Involves repeating organic or inorganic molecular

units.
Nanowires have following advantages:The ability to create highly conductive nanowires because electrodeposition relies on electron transfer, which is the fastest along the
highest conductive path.
Electro-deposited nanowires tend to be dense continuous and highly
crystalline in contrast to other deposition methods.
The ability to control the aspect ratio of the metal nanowires by
monitoring the total amount of passed charge.

Abstract
We briey reviewed the existing research on the Eco toxicity of
nanowires and suggested directions for further study. Nanowires are
technological innovations that can benet humans. However, it is
important to consider the effects of nanowires on the environment.
Only a few studies have reported acute and chronic ecological
toxicity of nanowires on aquatic and terrestrial organisms, and limited
research papers have reported antibacterial effects of nanowires. It is
assumed that nanowires have a toxic mechanism similar to that of
nanoparticles or ions, but the mechanism remains unknown because
so little research has been conducted on the ecological toxicity of
nanowires. More in-depth assessments of the chronic toxicity,
bioavailability, cytotoxicity, and genotoxicity of nanowires on various
species are needed.

Introduction
Nano materials are widely used in the electronic, chemical, and
medical industries and play a role in the global development of
industry. The properties of nanomaterial differ from those of bulk
materials and ions. Nano materials have various shapes, including
Nano spheres, Nano rods, nanotubes, nanowires, Nano disk,
nanolms, nanolaments, and Nano plates. They may be zero
dimensional (0D), one dimensional (1D), two dimensional (2D), or
three dimensional (3D). Nano spheres, nanoparticles, and quantum
dots are dened as 0D nanomaterial. Nanowires, Nano rods,
nanotubes, Nano belts, and Nano ribbons are 1D nanomaterial,
whereas nanowire arrays, nanowire fabrics, Nano disks, nanolms,
Nano plates, Nano sheets, Nano walls, nanobers, and Nano prisms
are 2D nanomaterial.

By denition, a nanowire is a wire with a Nano scale diameter.

Nanowires have potential applications in the biomedical and clinical
industries as antibacterial agents, as sensors of metals, in solar cells,
in the removal of metals and in energy storage. The number of uses of
nanowires continues to increase, and a number of toxicological
studies on human or mammalian cells have conrmed the
biocompatibility and biosafety of various nanowires. These studies
examined silver nanowires zinc oxide nanowires, titanium dioxide
nanowires, nickel nanowires, magnetic nanowires, silica nanowires,
iron nanowires, tellurium nanowires, and cerium nanowire.
Because nanowires can be released into the environment, Eco
toxicological studies of nanowires have also been conducted. In this
brief review, reports of the eco toxicological effects of nanowires and
nanowire arrays were collected and intensively reviewed, and the
need for future studies to assess the safety of nanowires was
examined. To the best of our knowledge, this is the rst review of the
eco toxicological effects of nanowires and is highly relevant to
ecological risk assessments of Nano materials by industries and
governments.

Nanowires
pollution)

effects

on

environment

(causing

Toxicity of nanowires to aquatic and sediment biota

There have been numerous reports of nanoparticles eco toxicity on
aquatic and sediment biota, but few eco toxicological studies of
nanowires have been conducted (Table 1). The toxicity of nanowires
has been evaluated in two sh species (Danio rerio and Oncorhynchus
mykiss), three crustacean species (Hyalella azteca, Daphnia similis,
and Daphnia magna), and three sediment-dwelling invertebrates

(Lumbriculus variegatus, Lampsilis siliquoidea, and Chironomus

dilutus). Mwangi et al. (2011) assessed the toxicity of silicon carbide
nanowires (SiC NWs) to sediment-dwelling invertebrates exposed
through water or sediment, using H. azteca, L. variegatus, L.
siliquoidea, and C. dilutus. When H. azteca were exposed to sonicated
or nonsonicated SiC NWs in hard water and sediment, no signicant
mortality was observed due to nonsonicated SiC NWs, but 0 %
survival was observed after exposure to the sonicated SiC NWs.
Mwangi et al. (2011) assumed that sonication broke the SiC NWs into
particles and caused surface hydroxylation that had fatal effects on H.
azteca. Otherwise, sediment-dwelling worms, mussels, and insects
that were exposed only to sonicated SiC NWs were not affected, even
by exposure for 96 h at a concentration of 1.0 g/L. This result
indicated that sediment-dwelling worms, mussels, and insects showed
less sensitivity than amphipod H. azteca to the sonicated SiC NWs.
Mwangi et al. (2011) also found that layering of SiC NWs on the
sediment surface induced more growth inhibition of H. azteca than
did mixing SiC NWs in the sediment because layered SiC NWs were
more available to the H. azteca than mixed SiC NWs in the sediment.
In tests of nanowires effects on sh embryos, silica nanowires (Si
NWs) (Nelson et al. 2010) and silver nanowires (Ag NWs) (George et
al. 2012) were fatal to zebrash embryos (D. rerio). According to
Nelson et al. (2010), Si NWs caused mortality of developing D. rerio
embryos at an LD50 of 110 pg/g and also induced birth defects
(teratogenicity) by interfering with neurulation and disrupting the
expression of sonic hedgehog. George et al. (2012) investigated the
different shapes of Ag nanomaterial (Nano spheres, nanowires, and
Nano plates), using D. rerio embryos and O. mykiss gill cells in vitro.
In the embryo test, Ag NWs did not affect hatching rate (48 hpf at 5
lg/ mL), but mortality was induced at 120 hpf at 5 lg/mL. In the in

vitro test, Ag NWs did not reduce cell viability but did cause potential
oxidative stress. Ag NWs were potentially acutely toxic to Daphnia.
Artal et al. (2013) studied the role of silver and vanadium release in
the toxicity of silver vanadate nanowires (AgVO3 NWs) to D. similis,
using AgVO3 NWs decorated with Ag NPs, and estimated the EC5048 h at 1 lg/L. Scanlan et al. (2013) investigated the acute toxicity of
different-sized and coated Ag NWs on D. magna and concluded that
short and SiO2-coated AgNWs were more toxic to this species than
were long or PVP-coated AgNWs. However, no correlation between
gene expression and LC50 was apparent.

Toxicity of nanowires to terrestrial biota

To date, only one article has reported the impacts of nanowires on
terrestrial organisms (Table 2). Adolfsson et al. (2013) investigated
the effects of bare and hafnium oxide-coated gallium phosphide
nanowires (GaP NWs) on the lifespan, fertility, rate of gene mutation,
and immune response of the fruit y, Drosophila melanogaster, using
a food-exposure approach. There were no changes of gene expression
or immune responses when D. melanogaster larvae were exposed,
until the third instar (8899 h). In addition, GaP NWs did not
signicantly affect lifespan or fecundity of adult ies, except for a
slight decrease in fertility at day 29, although the test subjects were
exposed chronically for 4958 days. Adolf son et al. (2013) detected a
slight decrease in fecundity when adult ies were exposed to hafnium
oxide-coated GaP NWs. In order to determine the acute and chronic
eco toxicity of nanowires to terrestrial organisms, many further
studies using various terrestrial species and exposure through soil
tests are needed.

Toxicity of nanowires to bacteria

As shown in Table 3, 18 studies have examined the antibacterial
properties of nanowires. The antibacterial effects of Ag-based NWs,
ZnO NWs, MgO NWs, Mn2O3 NWs, Tibased NWs, and CdO NWs
were evaluated. Test subjects included the pathogenic bacteria species
Escherichia coli, Bacillus subtilis, Staphylococcus aureus,
Table1

Table#2

Enterococcus faecalis, Salmonella enterica, Candida albicans, and

Aspergillus Niger. All studies shown in Table 3 assessed growth
inhibition, and some studies also calculated the maximal inhibitory
concentration (MIC) and minimal bactericidal concentration (MBC)
of tested nanowires by performing MIC and MBC tests. Although test
methods, tested nanowires, exposure concentration, exposure
duration, medium, and tested bacteria strains varied, the research
studies demonstrated the potential antibacterial properties of each
nanowire. However, it is not well conrmed that nanowires have
adverse effects on environmentally important and benecial microbial
communities when nanowires are released into the environment.

Antibacterial properties of nanowire arrays and

fabrics:
A range of types of nanowires have applications as nanowire arrays
and fabrics. Table 4 presents the literature evaluating the eco toxicity
of nanowire arrays or fabrics. These studies investigated the
antibacterial properties of nanowire arrays or fabrics to eliminate
pathogenic bacteria species in antibacterial applications.
Unfortunately, the eco toxicological effects of nanowire arrays and
fabrics on aquatic and terrestrial organisms have not been studied.
Three studies tested the effects of Si NW arrays, and one study tested

the effects of ZnO NW arrays on organisms. Wang et al. (2007)

reported that well-dened, less-oriented or randomly oriented ZnO
NW arrays reduce the survival of E. coli after a 90-min exposure.
Wang et al. (2011) conrmed that Si NW arrays modied with
quaternized poly (2-(dimethyl amino ethyl) methacrylate)
(pDMAEMA) led to high bacterial adhesion and cell death of E. coli
after an 18-h exposure. Fellahi et al. (2013) reported that Si NW
arrays decorated with AgNPs or CuNPs showed antibacterial activity
after a 24-h exposure and induced leakage of sugars and proteins
from the cell membranes of bacteria, reducing cell viability. Li et al.
(2014) observed antibacterial effects of Si NW arrays on E. coli, B.
subtilis, and S. aureus.
Davoudi
et
al.
(2014)
synthesized
silver-7,7,8,8tetracyanoquinodimethane nanowire fabrics and conrmed that they
have potential antimicrobial applications by observing antibacterial
effects on E. coli and Staphylococcus albus.

Toxic mechanism of nanowires:

Demonstrations of the toxicity level and the relative contributions of
dissolved ions and nanomaterials are important in order to understand
the toxic mechanisms in Nano toxicology. However, studies have
reported different results for the relative contribution to toxicity of
dissolved ions from nanowires and from nanomaterial themselves.
Davoudi et al. (2014) observed that Ag NW fabrics possessed
antibacterial properties. Visnapuu et al. (2013) reported that dissolved
Ag ions from Ag NWs caused toxic effects on microorganisms, after
conducting an analysis with AAS. Jiang et al. (2012) reported that
released Ag ions from Ag-doped trimolybdate nanowires caused toxic
effects and produced reactive oxygen species (ROS) in bacteria. In
the studies reporting bactericidal properties of nanowires, the way in

which nanowires reduced cell viability was conrmed. Nataraj et al.

(2014) observed that TiO2 NWs disrupted the membrane potential of
S. aureus. Fellahi et al. (2013) conrmed that Si NWs induced the
leakage of sugars and proteins from the cell membrane. AlHazmi et
al. (2012) reported that MgO NWs broke bacterial cell membranes
and damaged E. coli cells. Mn2O3 NWs were also observed to
disrupt E. coli cell membranes and to cause leakage of intracellular
contents in a study that used TEM analysis (Hassan et al. 2012).
According to Zhang et al. (2007), the effects of Ag NWs on bacteria
may be similar to those of Ag, which has strong antibacterial activity
and inactivates bacterial proteins by interacting with the -SH group in
the bacterial protein molecules. Likewise, Wang et al. (2007)
speculated that the toxic mechanism of ZnO NW arrays affecting
bacteria was similar to the toxic mechanism of ZnO NPs, which are
broadly known to generate ROS.
Table#3: An overview of studies with NW on antibacterial properties.

However, there is limited information regarding the toxic mechanism

of nanowires in aquatic and terrestrial organisms. Ag NWs generated
superoxide in O. mykiss gill cells and affected the survival rates of D.
rerio embryos (George et al. 2012). Si NWs also killed developing D.
rerio and induced teratogenicity by interfering with neurulation and
disrupting the expression of sonic hedgehog (Nelson et al. 2010).
Because limited ecological toxicity tests have been conducted, the
toxic mechanisms of nanowires are still under investigation and
require further research.

Environmental pollution:
Nano pollution is a generic name for waste generated by Nano or
during the nanomaterial manufacturing process. Eco toxicological
impacts of nanoparticles and the potential for bioaccumulation in plants
and microorganisms is a subject of current research, as nanoparticles are
considered to present novel environmental impacts. Of the US$710
million spent in 2002 by the U.S. government on nanotechnology
research, $500,000 was spent on environmental impact assessments.
Nano waste is mainly the group of particles that are released
into the environment, or the particles that are thrown away when still on
their products. The thrown away nanoparticles are usually still
functioning how they are supposed to (still have their individual
properties), they are just not being properly used anymore. Most of the
time, they are lost due to contact with different environments. Silver
nanoparticles, for example, they are used a lot in clothes to control odor,
those particles are lost when washing them. The fact that they are still
functioning and are so small is what makes Nano waste a concern. It can
float in the air and might easily penetrate animal and plant cells causing
unknown effects. Due to its small size, nanoparticles can have different

properties than their own material when on a bigger size, and they are
also functioning more efficiently because of its greater surface area.
Most human-made nanoparticles do not appear in nature, so living
organisms may not have appropriate means to deal with Nano waste.
The capacity for nanoparticles to function as a transport
mechanism also raises concern about the transport of heavy metals and
other environmental contaminants. Two areas of concern can be
identified. First, in their free form nanoparticles can be released into the
air or water during production, or production accidents, or as waste byproduct of production, and ultimately accumulate in the soil, water, or
plant life. Second, in fixed form, where they are part of a manufactured
substance or product, they will ultimately have to be recycled or
disposed of as waste.
Scrinis raises concerns about Nano-pollution, and argues
that it is not currently possible to precisely predict or control the
ecological impacts of the release of these Nano-products into the
environment. A May 2007 Report to the UK Department for
Environment, Food and Rural Affairs noted concerns about the
toxicological impacts of nanoparticles in relation to both hazard and
exposure. The report recommended comprehensive toxicological testing
and independent performance tests of fuel additives. Risks have been
identified by Uskokovic in 2007. Concerns have also been raised
about Silver Nano technology used by Samsung in a range of appliances
such as washing machines and air purifiers.
One already known consequence to metals exposure is
shown by silver, if exposed to humans in a certain concentration, it can
cause illnesses such as agrarian and argyrosis. Silver can also cause
some environmental problems. Due to its antimicrobial properties

(antibacterial), when encountered in the soil it can kill beneficial bacteria

that are important to keep the soil healthy. Environmental assessment is
justified as nanoparticles present novel environmental impacts. Scrinis
raises concerns about Nano-pollution, and argues that it is not currently
possible to precisely predict or control the ecological impacts of the
release of these Nano-products into the environment.
Metals, in particular, have really strong bonds. Their
properties follow up to the Nano scale as well. Metals can stay and
damage the environment for a long time, since they hardly degrade or
get destroyed. With the increase in use of nanotechnology, it is predicted
that the Nano waste of metals will keep increasing, and until a solution
is found for that problem, that waste will keep accumulating in the
environment. On the other hand, some possible future applications of
nanotechnology have the potential to benefit the environment. Nano
filtration, based on the use of membranes with extremely small pores
smaller than 10 nm (perhaps composed of nanotubes) are suitable for a
mechanical filtration for the removal of ions or the separation of
different fluids. A couple of studies have found a solution to filtrate and
extract those nanoparticles from water. The process is still being studied
but simulations have been giving a total of about 90% to 99% removal
of Nano waste particles from the water at an upgraded waste water
treatment plant. Once the particles are separated from the water, they go
to the landfill with the rest of the solids. Furthermore, magnetic
nanoparticles offer an effective and reliable method to remove heavy
metal contaminants from waste water. Using Nano scale particles
increases the efficiency to absorb the contaminants and is comparatively
inexpensive compared to traditional precipitation and filtration methods.
One current method to recover nanoparticles is the Cloud Point
Extraction. With this technique, gold nanoparticles and some other types
of particles that are heat conductors are able to be extracted from

aqueous solutions. The process consists of a heating section of the

solution that contains the nanoparticles, and then centrifuged in order to
separate the layers and then separate the nanoparticles.

Conclusions:
It is important to understand whether nanomaterial, including nanowires,
pose a risk to the environment, but so far, there are limited studies of this
area. Only 24 eco toxicological studies of nanowires have been reported
since 2007, and most of them were conducted since 2010. Many more
studies of ecotoxicology have been conducted on nanoparticles than on
nanowires. The most studied nanowire was Ag NW (15 citations),
followed by Si NW (2 citations), ZnO NW (2 citations), TiO2 NW (1
citation), MgO NW (1 citation), Mn2O3 NW (1 citation), CdO NW (1
citation), and GaP NW (1 citation). A number of studies have focused on
the antibacterial capabilities of nanowires to evaluate their potential
applicability in medicine; however, the impacts of nanowires on
environmentally important microbial communities and ecosystems are
poorly understood. Additionally, few studies conrmed modes of
toxicity of nanowires or contribution of ion toxicity dissolved from
nanowires.
The following types of studies are needed in order to assess the
ecological effects of nanowires:
Ecological toxicity data regarding aquatic and terrestrial
organisms. The existing literature is insufcient and consists
mainly of studies of microbial organisms. Reliable endpoint values
(LCx, ECx, LOEC, NOEC) are also needed.
Genotoxicity and cytotoxicity of nanowires. The mechanism of
toxicity to organisms, particularly terrestrial ones, is not clear.

Understanding genotoxic effects and cellular effects can provide

clues to the mechanism.
Bioavailability of nanowires to organisms (e.g., bioaccumulation
studies, depuration studies). It is important to assess the fate of
nanowires in the environment.
Chronic effects of nanowires. Very limited results were reported
for this topic.
Although we are challenging to conrm the risk of nanomaterial
including nanowires, there are limited eco toxicological results to protect
the ecosystem. We suggest further eco toxicological testing of nanowires
be conducted in order to protect the environment before nanowires are
widely commercialized.
Pollutants emitted by factories and car exhausts affect humans who
breathe in these harmful gases and also aggravate climate change up in
the atmosphere. Being able to detect such emissions is a critically
needed measure.
New research by the Nanoparticles by Design Unit at the Okinawa
Institute of Science and Technology Graduate University (OIST), in
collaboration with the Materials Center Leoben Austria and the Austrian
Centre for Electron Microscopy and Nano analysis has developed an
efficient way to improve methods for detecting polluting emissions
using a sensor at the Nano scale. The paper was published
in Nanotechnology.
The researchers used a copper oxide nanowire decorated with palladium
nanoparticles to detect carbon monoxide, a common industrial pollutant.
The sensor was tested in conditions similar to ambient air since future
devices developed from this method will need to operate in these
conditions.

Copper oxide is a semiconductor and scientists use nanowires fabricated

from it to search for potential application in the microelectronics
industry. But in gas sensing applications, copper oxide was much less
widely investigated compared to other metal oxide materials.
A semiconductor can be made to experience dramatic changes in its
electrical properties when a small amount of foreign atoms are made to
attach to its surface at high temperatures. In this case, the copper oxide
nanowire was made part of an electric circuit. The researchers detected
carbon monoxide indirectly, by measuring the change in the resulting
circuit's electrical resistance in presence of the gas. They found that
copper oxide nanowires decorated with palladium nanoparticles show a
significantly greater increase in electrical resistance in the presence of
carbon monoxide than the same type of nanowires without the
nanoparticles.
The OIST Nanoparticles by Design Unit used a sophisticated technique
that allowed them to first sift nanoparticles according to size, then
deliver and deposit the palladium nanoparticles onto the surface of the
nanowires in an evenly distributed manner. This even dispersion of size
selected nanoparticles and the resulting nanoparticles-nanowire
interactions are crucial to get an enhanced electrical response. The OIST
nanoparticle deposition system can be tailored to deposit multiple types
of nanoparticles at the same time, segregated on distinct areas of the
wafer where the nanowire sits. In other words, this system can be
engineered to be able to detect multiple kinds of gases. The next step is
to detect different gases at the same time by using multiple sensor
devices, with each device utilizing a different type of nanoparticle.

Compared to other options being explored in gas sensing which are

bulky and difficult to miniaturize, nanowire gas sensors will be cheaper
and potentially easier to mass produce.
The main energy cost in operating this kind of a sensor will be the high
temperatures necessary to facilitate the chemical reactions for ensuring
certain electrical response. In this study 350 degree centigrade was used.
However, different nanowire-nanoparticle material configurations are
currently being investigated in order to lower the operating temperature
of this system.
"I think nanoparticle-decorated nanowires have a huge potential for
practical applications as it is possible to incorporate this type of
technology into industrial devices," said Stephan Steinhauer, a Japan
Society for the Promotion of Science (JSPS) postdoctoral research
fellow working under the supervision of Prof. Mukhles Sowwan at the
OIST Nanoparticles by Design Unit.