Session No.

507

Updating Nanotechnology for the EHS Professional for 2014

Amanda Archer, CSP, CIH

Lockheed Martin Aeronautics
Ft. Worth, Texas
John Baker, CIH
Bureau Veritas North America
Houston, Texas

Introduction
Nanoparticles are nothing new
While the term nanotechnology is a modern term, the use and applications of nano sized materials dates
back to ancient Roman times. The Lycurgus Cup is an excellent example of 4th century artisans
exploiting nano sized materials for its unique properties. The glass used in this cup contains gold and
silver nanoparticles dispersed throughout. When light shines from the back, the glass appears red, when
illuminated from the front, the glass appears green. (Kulinowski, 2014) In medieval Europe, nanoscale
gold was used in stained glass and nanotubes were found in blades of swords made in Damascus.
Additionally there are many naturally occurring nano sized particles. Ultrafine dust particles from dust
storms, volcanoes, sea salt spray are all examples of naturally occurring nano sized particles. In eastern
Europe the unique micro climate of salt mines are a common way to treat asthma (Christina Buzea, 2007).
There are other more familiar nano sized particles that are incidental to industry. A few examples of these
are diesel particulate, welding fumes and dust from sand blasting. For these familiar nano-scale and
ultrafine particles we have devised effective means of control.

Engineered nanoparticles are new

Engineered nanoparticles are new to us and may pose slightly different challenges because of size and
chemical effects such as reactivity and physical properties such as electrical conductivity due to the
uniform size of these particles. In 1959 pioneering physicist Richard Feynman lectured, There is Plenty
of Room at the Bottom. He was interested at manipulating matter at the atomic scale particularly for
applications in computers. At the conclusion of the lecture Feynman posed two challenges with cash
awards associated with them. The first was to construct a tiny motor which was accomplished in 1960 and
the second was to scale down the Encyclopedia Britannica so small it would fit on the head of a pin, the
first two pages of, A Tale of Two Cities was scales down to the size of a head of a pin in 1985. (Gribbin
& Gribbin, 1997) This ushered in a new type of manufacturing and approach to material science.
When discussing nanotechnology, nanomanufacturing is a critical part of the subject . In
manufacturing there are two basic approaches, either top down or bottom up. Top down approaches like
milling a solid piece of aluminum for a product reduce materials down to the nanoscale. This approach

requires large amounts of material and can lead to waste if excess material is discarded. Conversely, the
bottom up approach creates products from the atomic and molecular scale components. The bottom up
approach reduces waste and improves specific properties through the manipulation of the individual
properties that makeup the material. Bottom up is really the only way that commercial nanoparticles are
made and that is because the self-assemble. Our manufacturing processes simply create the optimal
environment for them to create themselves.
Engineered nanomaterials are intentionally produced to have at least one primary dimension less
than 100 nm. A nanometer is one-billionth of a meter, about 7 times the diameter of a neutral carbon
atom. (http://www.webelements.com/carbon/atom_sizes.html) For particles of this size, most of the atoms
or molecules are on the surface of the structure and quantum effects influence the way the atom within
the structure interact with light and other forms of electromagnetic radiation. This is where unique
phenomena enable novel applications and materials that can be stronger, lighter, more durable, waterrepellent, anti-reflective, self-cleaning, ultraviolet, infrared, antifog, antimicrobial, scratch-resistant, or
electrically conductive, among other traits (United States National Nanotechnology Initiative).

Advantages and Disadvantages of Novel Chemical and Physical

Properties
There are currently over 1000 consumer products that contain nano materials on the market today.
Current consumer products where nanomaterials are being used are the automobile industry to make cars
lighter and stronger, textiles industries to make fabrics stain resistant. Other applications include thin
films on eyeglasses and windows that can make them water repellant and scratch resistant. Additionally,
cosmetics and sunscreens are incorporating nanotechnology to provide better clarity and coverage as well
as properties of anti-microbial and antioxidation to help prevent premature aging (United States National
Nanotechnology Initiative). The unique properties of nanoparticles have also led to improvements in
medical imaging and treatment by creating vehicles for carrying the right therapy to the exact diseased
tissue with minimal disruption or harm to healthy tissue.
The exploitation of nanotechnology and nano materials is helping answer some of the worlds
real problems. New and renewable sources of energy have been a top priority for scientist for several
years. Incorporating nanotechnology into solar panels are producing more efficient designs in converting
sunlight to electricity, promising inexpensive solar power in the future. Additionally, nanotechnology is
helping to supply affordable, clean drinking water through rapid, low-cost detection of impurities in and
filtration and purification of water. Scientists believe that nanotechnology can help reduce and eliminate
airborne pollutions. In the future nano enabled sensors will be able to detect, identify, and filter out
harmful chemical or biological agents in the air. (United States National Nanotechnology Initiative).
The same thing that gives nano materials advantage is the same thing that can be a
disadvantageous. As these nano particles get smaller and smaller the behavior changes. Materials that are
inert at the macro size become catalysts at the nano size. Examples like platinum in the bulk phase is inert
but in a nano state is a catalyst. Aluminum also becomes combustible at the micro and nano size and gold
turns into a liquid at the nano size. The other important aspect of this science is surface area.
Nanomaterial compared to the same mass of material in bulk form has significantly greater surface area.
This can make this material more chemically reactive and bioavailable.

Need for a Balanced View of Hazard and Risk

Engineered nanomaterials are among the most studied subjects in occupational and environmental
toxicology today. A brief internet search in March 2014 reveals 150,000 various publications on nano
toxicology papers in recent years. There is concern that nanotechnology is unsafe, but the reality is
nanotechnology is safety neutral. Focusing only on the concept of nanotechnology rather than the
specific properties of individual nanomaterials can lead safety professionals to the assumption that there is
a common nano problem that can be solved using a common solution. The unique properties at the nano
scale differ among different kinds of nanoparticles and safety professionals should examine each particle
in terms of use, handling and disposal of the specific materials they are using.

Rationale for Material Characterization

The two examples of titanium dioxide (TiO2) and carbon nanotubes (CNT) are somewhat different in
their mechanisms of toxic effects. Although both these materials are considered nano materials the use,
application and handling of these materials is completely different. It is essential to determine the
chemical and physical properties of the nanoscale material to the extent possible before designing the
exposure assessment strategy. The safety professional should request as much information as possible
from the material scientists who have developed the nanomaterial. The properties of interest for
commercial development of a nanomaterial, including particle dimensions, degree of agglomeration or
aggregation, electromagnetic, thermal and optical properties, may be helpful in deciding what exposure
measurement techniques to use and how to best establish controls to protect workers from exposure.
Carbon nanotubes (CNT) are nanoscale cylinders of carbon (essentially consisting of seamlessly
rolled sheets of graphene) that can be produced with very large aspect ratios. Single-walled carbon
nanotubes (SWCNT) consist of a single rolled graphene sheet and have a typical diameter of
approximately 1 nm. Multi-walled carbon nanotubes (MWCNT) consist of several cylinders stacked
inside one another, and can have outer diameters ranging from less than 10 to more than 80 nm, Both
SWCNT and MWCNT can have lengths from 1,000 to 50,000 nm.
(http://www.cheaptubes.com/default.htm). Currently there are no studies reported in the literature of
adverse health effects in workers producing or using carbon nanotubes (CNT) or carbon nanofibers
(CNF). However there is great concern about inhalation CNT and CNF. The current NIOSH
recommended exposure limit (REL) is 1 g/m3 measured as respirable elemental carbon (Not necessarily
actual CNT). Aspiration of SWCNT are known to cause inflammation and damage to lung tissues as well
as create granulomas and fibrosis in animal studies. Several studies in rodents have shown an equal or
greater potency of CNT compared to other inhaled particles known to be hazardous to exposed workers
like ultrafine carbon black, crystalline silica, and asbestos. The results of several studies indicate that
CNT and CNFs have toxic effects such as fibrosis of the respiratory tract and lungs, and creation of
inflammation and oxidative stress (E.R. Kisin a, 2011), (Ashley R Murray1, 2012). For this reason free
and unbound CNT and CNF should be controlled as low as reasonably achievable.
Dermal exposure for CNT and CNF is less straightforward. To date there are no known cases of
human dermal toxicity contributed to CNF or CNT and limited information is available to accurately
assess the exposure. Topical application of SWCNT in large doses to mice resulted in inflammation that
was localized around or within the hair follicles; no significant changes were observed at the lower doses
tested (Murray AR, 2009). Pauluhn found no evidence of acute skin irritation or sensitization of
MWCNT (Baytubes) when tested on rabbits (2010). Given the limited amount of data on dermal
exposure to CNT and CNF, it would be prudent to wear protective clothing and gloves when it is
impossible to eliminate or control the release of exposure to CNT. Additionally, special care should be
taken to prevent CNT and CNF exposure to abraded or lacerated skin.

Titanium dioxide (TiO2), is an insoluble white powder used extensively in many commercial
products, including paint, cosmetics, plastics, paper, and food, as an anticaking or whitening agent. TiO2
is produced and used in the workplace in varying particle size fractions including fine (which is defined in
the 2011 NIOSH Current Intelligence Bulletin 63 as all particle sizes collected by respirable particle
sampling) and ultrafine (defined as the fraction of respirable particles with a primary particle diameter of
<0.1 m [<100 nm]). Particles <100 nm are also defined as nanoparticles. NIOSH recommends airborne
exposure limits of 2.4 mg/m3 for fine TiO2 and 0.3 mg/m3 for ultrafine (including engineered nanoscale)
TiO2, as time-weighted average (TWA) concentrations for up to 10 hr/day during a 40-hour work week.
These recommendations represent levels that over a working lifetime are estimated to reduce risks of lung
cancer to below 1 in 1,000. The recommendations are based on using chronic inhalation studies in rats to
predict lung tumor risks in humans. While NIOSH concludes that there is insufficient evidence to classify
fine TiO2 as a potential occupational carcinogen, NIOSH is concerned about the potential carcinogenicity
of ultrafine and engineered nanoscale TiO2 if workers are exposed at the current mass-based exposure
limits for respirable or total mass fractions of TiO2. NIOSH recommends controlling exposures as low as
possible, below the RELs.
Dermal exposure is also being studied particularly for cosmetics that contain substances such as
nano titanium dioxide. Studies to date show that TiO2 does not penetrate the outer layer of healthy,
undamaged skin.
Functionalizing nanoparticles with OH or other chemical groups can have a major influence
on increasing or reducing the toxicity. This has brought forward some concerns that the property that
gives TiO2 the light scattering and absorption properties can also harm damaged sunburnt skin.
Investigations on this are currently being conducted. NIOSH considers that coating nano TiO2 with other
materials appears to increase toxicity. However, functionalizing CNT appears to reduce toxicity. The
functionalization of CNTs improves their solubility and biocompatibility and alters their cellular
interaction pathways, resulting in much-reduced cytotoxic effects. (Vardharajula et al, Int J
Nanomedicine, 2012, 7:5362-5374) A recent study by NIOSH showed that MWCNT functionalized with
carboxyl groups (-COOH) significantly reduced the bioactivity and pathogenicity. (Sager et al,
Nanotoxicology, 2014, 8:(3), 317-327)

A Common Mistake that HSE Professionals Make

A common mistake that health and safety professional make in assessing nanomaterial hazards and risks
is assuming that the worker or the member of the public are exposed to primary particles, in other
words, the smallest individual nanoparticle making up the basic constituent of the nanomaterial. In reality,
it is very difficult to keep individual primary nanoparticles from combining into larger, but still of
respirable size structures called agglomerates and aggregates. The large surface area of nanoparticles
makes them very susceptible to attractive electrostatic and similar forces that cluster them together. Even
if the nanoparticles are not in freely flowing air, they cluster together because Brownian movement
impacts them together. This is a major reason why we must be careful in interpreting the results of the
toxicological studies. Toxicologists set up their experimental equipment to break up or otherwise disperse
the agglomerates and aggregates of nanoparticles into individual particles immediately before they are
introduced into the experimental animal or in vitro cell culture. Also, be sure to note the concentration of
the nanoparticles that are challenging the test system. Often these are orders of magnitude greater than the
actual concentrations that are measured in the workplace or the ambient environment.

Another Common Mistake that HSE Professionals Make

The failure to critically review the Material Safety Data Sheet (MSDS) or as they are called under the
Globally Harmonized System of Classification and Labeling of Chemicals (GHS), Safety Data Sheet for
nanomaterials with an eye to whether the properties of the actual nanomaterial are the basis of the hazard

classification rather than the properties of the bulk parent material is another common mistake.
Researchers found that among MSDSs obtained in 2010 2011 from 44 manufacturers, 67% provided
insufficient data for communicating the hazards of engineered nanomaterials. The most common
deficiencies were a failure to use numerical references or ranges to specify that the material is in the <100
nm size range, and a failure to provide toxicological data specific to the nanomaterial or to note that
nanomaterials may have different toxicities than larger particles of the same material (Eastlake, A., A
critical evaluation of material safety data sheets (MSDSs) for engineered nanomaterials. J. Chem. Health
Safety 2012).
The United Nations panel that governs changes to the GHS has stated that a distinct hazard
classification for nanomaterials will not be created, but will instead create guidance for how
manufacturers, importers and employers would apply existing classification criteria to hazardous
nanomaterials. Typical health hazard classes under GHS include such effects as acute toxicity,
carcinogenicity, mutagenicity, reproductive toxicity and specific target organ toxicity such as pulmonary
fibrosis.

Evaluation Methods
Once you have accurately understood the material you will be using and identified the operations that are
likely to produce exposure it is important to establish a safety program and protocol. NIOSH has
published a suite of references that are useful for medical monitoring protocol, safety in laboratories and
engineering controls for downstream handing and processing. These references can be found at
http://www.cdc.gov/niosh/topics/nanotech/pubs.html. Safety professionals are often times tasked with the
evaluation and control of particular hazards in the workplace. The next sections are dedicated to the
evaluation and control of nano particles in the workplace.

Real Time Detection Methods Exist, But They Are Not Specific to Nanoparticles or to
Condensation particle counters
Condensation particle counters make particles as small as 10 nm into droplets of condensed alcohol or
water about 100 times larger (1 micrometer) and counts each condensed droplet.
Condensation particle counters (CPC) are direct-read instruments used to measure particles in the
size range of 10 nanometers (nm) to 1000 nm. Data output is expressed as total number of particles per
cubic centimeter of air (P/cc). Has the ability to detect particles in the 10 to 100 nm range, even though it
will respond to the presence of larger particles. A CPC allows the safety professional to use a control area
and compare the results to make decisions in real time. A CPC counts all particles in the size range and
does not discriminate between types of particles. Also, non-spherical particles and agglomeration state
may cause variability in the precision and accuracy of optical-based counting instruments. To avoid
misleading conclusions it is important to compare particle concentration number within the instrument
and not from instrument to instrument or convert measurements to a common denominator in the attempt
to compare to a REL or PEL.
Optical Particle Counters
Optical particle counters (OPC) measure both mass and size fraction of airborne particulate using laser
light scattering. This instrument was used to estimate the aerosol mass concentration of particulate less
than 15,000 nm in aerodynamic diameter. It should be noted that aerosol photometers provide estimates
based upon assumed density and particle size distributions. Some instruments will respond to particles in
the size range of 100 nanometers (nm) to 15,000 nm and aerosol mass concentrations ranging from 1 to
150,000 g/m3. However, detector sensitivity drops dramatically below 250 nm diameter and its
efficiency in measuring fiber-like aerosols is less than that obtained when sampling an aerosol composed
of spherical particulate.

There is only one authoritative standard that has been recommended for particle number
concentrations: BSI recommends restricting exposure when the particle number concentration exceeds
20,000 particles/cc greater than background.
Diffusion Chargers and Photoelectric Aerosol Sensors
Diffusion chargers and photoelectric aerosol sensors measure particle surface area and total particle
bound polycyclic aromatic hydrocarbons (PAHs) respectively. In the diffusion charger, a corona
discharge produces ions in the carrier gas; the ions attach to the surface of the particles by diffusion; the
particles are collected in an electrically insulated filter and the electric current flowing from the filter is
measured as the active particle surface area. In the photoelectric aerosol sensor, a UV lamp
photoionizes carbonaceous particles which are collected electrically by an insulated filter; the electric
current flowing from the filter is measured as the total particle bound PAH. These instruments are
desktop sized units that are better suited to area sampling than to personal breathing zone sampling.
Another possible drawback is that while the results can be used for relative comparisons of these
measured values, there are not any established exposure limits for these parameters at this time.
Scanning Mobility Particle Sizer (SMPS) and Electrical Low Pressure Impactor (ELPI)
The scanning mobility particle sizer is often used in research studies for material characterization. It uses
a differential mobility analyzer in combination with a CPC to measure ultrafine particles down to the
single nanometer size range. The differential mobility analyzer uses a corona discharge to electrically
charge the particles to be measured as they flow along a negatively charged inner cylindrical electrode,
which can be set to various voltages which is set inside a positively charged outer cylinder. Positively
charged particles travel along the electrode while negatively charged particles deposit on the outer
cylinder. Very small particles with high mobilities move rapidly down the center electrode and deposit.
Larger particles deposit further along the rod while still larger ones pass out the bottom of the classifier
with the main air flow. A narrow range of particle sizes is removed with the air flowing through the exit
slit at the bottom of the classifier. This particle concentration is measured by the CPC. (Sheldon K.
Friedlander, Smoke, Dust and Haze: Fundamentals of Aerosol Dynamics 2nd ed., Oxford Univ. Press,
2000.) The electrical low pressure impactor (ELPI) combines the principle of charging the airborne
particles with collection on a set of ever-smaller orifice plates as described in the next section. Both of
these are laboratory instruments that require line current, and while suited for research or area monitoring,
are not useful in field studies of personal breathing zone exposure.
However, at least one handheld diffusion charger/electrometer instrument is commercially
available in Europe and reports in the peer-reviewed literature indicate that this technology may be useful
for ambient air or personal exposure assessment. (Asback et al., Ann Occ Hyg, 2012; Meier et al. Aerosol
Sci Tech, 2013).

Filter-Based Methods Requiring Laboratory Analysis

Particle-sizing Collectors
Respirable particle cyclones can be used to collect particles with a median aerodynamic diameter less
than 4,000 nm onto a filter for laboratory chemical analysis or electron microscopic examination.
Cascade impactors separate particles into size ranges by sequentially drawing the air through a
series of orifices. The particles passing through the initial stage either impact onto a plate (usually coated
with a grease to prevent captured particles from bouncing off) and the smaller particles follow the
streamlines around the edge of the plate through a smaller orifice followed by another plate, etc.
Sequential collection of ever smaller size particles are affected at each stage of the cascade. Special

cascade impactors, termed micro-orifice uniform deposit impactors (MOUDIs), have been developed that
can separate particles less than 25 nm if operated at 30 liters per minute.
A combination cyclone and personal cascade impactor is under development in Taiwan that can
collect both respirable size particles and nanoparticles simultaneously (Tsai, C-J et al, Environ Sci Tech,
2012), which may be useful in the future for both ambient and personal air sampling.
Examination by Light and Electron Microscopy
The use of both optical and electron microscopy to assess exposure potential is commonplace in the
analysis of asbestos and similar fibrous particulate. The NIOSH 7400 method used for counting asbestos
fibers requires the use of an optical phase contrast microscope with a special graticule that divides the
image into various fields for counting. The method does not specifically identify asbestos, but requires
fibers with a diameter less than 3 micrometers (m) and longer than 5 m with a length to width ratio of
3:1 to be counted. At least 20 fields, each representing an area of 0.00785 mm2, up to 100 fields must be
examined, and fibers are selected for counting based on a set of rules specified in the method. A
transmission electron microscope (TEM) method, NIOSH 7402, can provide positive identification, shape
and structure of asbestos and was designed to be used with the 7400 optical method.
Due to their small size, individual or primary nanoparticles can only be directly observed using
high resolution techniques, either field-emission scanning electron microscopy (FE-SEM) or transmission
electron microscopy (TEM). In special cases, polarized light optical microscopy can be used for
screening large numbers of fields to assist in selection of fields for electron microscopy. The high
magnifications available with electron microscopy means that the area of the field being observed is
extremely small, and therefore, a very large number of fields would need to be examined to characterize
the sample collected on a typical 37 mm or 25 mm filter. Thus, the number of fields that must be
examined to count nano-scale particles by electron microscopy is prohibitive for most budgets and time
schedules. However, electron microscopy provides unique benefits to characterize the shape, surface
texture and degree of agglomeration or aggregation of particulate. An SEM scans the surface of the
particle with an electron beam while the TEM shoots the electron beam through the particle. These
techniques are complementary to provide a more complete picture of the particle than either technique
alone. The SEM can be paired with energy dispersive x-ray spectrometry to perform chemical elemental
analysis of nanoparticles and associated catalyst metals, and Raman spectroscopy to explore molecular
vibrational frequencies for fingerprinting specific materials. The TEM can provide a higher resolution,
akin to a higher magnification than an SEM, and gives a better picture of the interior of an object.

Consumer Product Testing

All the Above Methods Used by EPA
Nanomaterials are being used in 500 consumer products and the number is expected to grow such that
consumer products that have been nano-enhanced will make up a $1 Trillion worldwide market by 2015
(EPA website at http://www.epa.gov/nanoscience/quickfinder/nanomaterials.htm).
EPA is working with the Consumer Product Safety Commission (CPSC) to study nanosilver used
in textiles and packaging for antimicrobial properties to reduce bacteria and odor; and also for micronized
copper wood preservatives.
The EPA is developing a test methodology to find out if nanoparticles embedded in the textile,
wood, other products may become released as the materials age and with use.

Control Methods
Hierarchy of Controls
Safety professionals have historically used a hierarchy of controls to rank feasible and effective
exposure controls. The most effective control, elimination of the hazard, is at the top of the hierarchy,
followed in turn by material substitution, engineering controls, administrative controls and, finally,
personal protective equipment (PPE).

Elimination
Elimination of the hazard is the most preferred method of control. For example, replacement of an
inspection task where containers of powdery nanomaterials are opened with transparent containers or a
technology that does not require opening of the containers is preferred.

Material Substitution
Material substitution is the next most preferred method. This being said, remember our discussion about
nanomanufacturing bottom up approach. This takes into consideration every molecule that goes into a
material. The material is designed or created to accentuate the special features of a nanomaterial. In many
cases the manufactured materials are the replacement because of its unique features. In material
substitution it can be recommended that materials are made with less of a nano material to make them
more safe for individuals who may have to work with them downstream. Additionally, materials can be
developed which encourage aggregation or agglomerations. In this way materials are less likely to
become loose and free particles.

Engineering Controls
The next most preferred control method is engineering controls. Engineering controls used in
pharmaceutical production are effective in nanoparticle control. Glove boxes are an excellent method for
keeping contaminates contained to a specific area and away from the workers breathing zone. Glove
boxes are totally enclosed working cabinets with gloves built into the cabinet to allow workers to
manipulate objects inside the box without coming in contact with the hazard. When using glove boxes it
is important to remember the worker and configure the work and the workplace to take into consideration
good ergonomics. Gloves bags commonly used in asbestos abatement are another effective tool for
containment. Glove bags can be utilized to contain a small working area. Some processes are too large for
these types of containment. In larger processes, total containment maybe necessary. Large-scale
containment systems are equipped with HEPA ventilation to prevent migration of particles beyond a
enclosed area should be utilized. These containment systems allow workers to enter in to the area and
conduct work. Negative pressure enclosures like those used in asbestos containment and abatement are
effective in controlling nano particles. Additionally in these areas where nanomaterials are used fiber
migration can prevented by having double enclosure doorways with downdraft. This system is designed
to act like an air shower to prevent workers from carrying nano particles with them when they leave an
area. Other effective methods of keeping contaminates isolated are the adhesive mats. An adhesive mat
has several layers of sticky polyethylene film that peel off for easy cleanup.
During packaging for shipping operations continuous liners help keep contaminates contained.
Similarly, continuous bagging can be used for the intermediate output from various processes and for
final products. A process discharges material into a continuous bag that is heat sealed after loading to
eliminate dust exposures caused by powder handling.

For materials outside of a containment environment ventilation is a very effective means of

protecting workers from particles exposure. Ventilation systems should be equipped with High
Efficiency Particulate Air (HEPA) filtration systems. Laboratory hoods are another good engineering
control designed to remove particulate from the breathing zone. A recent study conducted by found that
constant velocity hoods are recommended for work on nano materials. Additionally, lab hood for nano
materials should have a low face velocity and a vertical air curtain just inside the hood, which can reduce
nanomaterial flowing out. Fume hoods should be operated with a face velocity between 0.4 and 0.6 m/s
(80120 ft/min) and sash heights should remain as low as possible when manipulating nanomaterials,
within this velocity range. (Su-Jung (Candace) Tsai, 2009).

Common Misunderstanding about Respirators

HEPA Air filtration is a technology that is often misunderstood. Particles are trapped by several
mechanisms in fabric filters including diffusion (Brownian motion), interception, impaction and
electrostatic attractions. The original HEPA filter was designed in the 1940s and was used in the
Manhattan Project to prevent the spread of airborne radioactive contaminants. HEPA filters are composed
of an array of randomly arranged fibers from .5 to 2.0 m. HEPA filter do not act like a sieve where
particles smaller than the largest opening can pass through. They are designed to target much smaller
pollutants and particles. Particles are trapped in several different ways depending on the particle size
moving through the interwoven fibers. The first is Interception. This is where the particle is following a
straight-line path in the airstream and comes within one radius of a fiber and adheres to the fiber. This is
typically responsible for collecting larger particles. The next is Impaction, where particles having too
much inertia due to its size or mass are unable to avoid fibers by following the curving contours of the air
stream and are forced to embed on one of them directly. For particles .4um and larger interception and
impaction are the major mechanism preventing particle penetration. For particles less than .1 m
Diffusion is the mechanism that entraps the particle. Small particles are constantly bombarded by air
molecules, which cause them to deviate from the airstream and come into contact with a filter fiber. In
between .4m and .1m is the most penetrating particle size (MPPS), .3m. This is the weakest point in
filter performance because both diffusion and interception are inefficient. Filter performance
specifications are determined at the MPPS size. When a manufacture states the a filter removes 99.97% at
the 3um particles size what they are really saying is that at the worst collection point the filter will remove
99.97% and it is more efficient at the larger particle size and the smaller particle size (Wikipedia, 2014).
In the downstream production and processing of nano materials there are several control methods
that proven to be effective and are very familiar to safety and health professionals. Handheld ventilation,
like HEPA vacuums, fume extractors and portable air cleaners are very effective in removing nano
particles from the working environment. Using wet cutting techniques commonly adopted for silica
control during construction activities has also been found to be effective in nano particle control. (Bello
D, 2009). NIOSH published DHHS (NIOSH) Publication No. 3014-102, Current Strategies for
Engineering Controls in Nanomaterial Production and Downstream Handling Processes, in November
2013. This is an excellent resource for anyone seeking to control nanomaterials in their workplace
(NIOSH Publications and Products, 2013).

Administrative Controls
Training may be the most effective of administrative controls for nano materials. Worker training should
include information on the hazards of the specific nano material they are working with. The information
should lend to understanding of the potential workplace exposures, potential health risks, routes of
exposure, and instructions for reporting health symptoms. Workers should be provided with information
about medical screening, the health benefits of the medical program, and the procedures involved.

Periodic medical evaluations should be performed. The evaluations should include a respiratory
symptoms update, an occupational and medical history update, a physical exam and if necessary
spirometry and chest x-rays.
After the material has been characterized periodic monitoring is important in assuring that
controls are effective and workers are adequately protected. Direct reading instruments can be a useful
tool in periodic monitoring.
Work procedures are another form of control that minimize and eliminate potential risk. Among
the work procedures routine evaluation should be conducted as well as procedures that require the worker
to check the engineering controls, e.g. measuring the face velocity of hoods before starting work and
logging the results. Additionally bag in/bag out procedures are a type of work procedure designed to
protect workers performing maintenance on air filter change out. A plastic liner is attached to a service
port on the filter unit when the filter is ready for replacement, the facility maintenance worker, wearing
appropriate PPE, removes the filter into a liner. This process contains the filter with its contaminants so
the worker is not exposed and the particulates (Filtration Group Inc).
Another work procedure that may be useful is to minimize the container size for manual material
handling. Minimizing the size of the container or using a long handled tool will prevent the worker from
having to bend over or reach far into the inside of a container in such a way that his breathing zone is
inside the container. NIOSH recommends a maximum container depth of 25 inches (Control of dust from
powder dye handling operations, DHHS (NIOSH) Publication No. 97-107,1997). If large containers are
required, engineering controls to provide a barrier between the container and the breathing zone of the
worker are recommended.
General work place hygiene is very important when working with nano materials. Facilities for
hand-washing and encourage workers to make use of these facilities before eating, smoking, or leaving
the worksite. When necessary provide showering facilities and locker-room, with separate facilities for
storage of non-work clothing, to prevent the inadvertent cross contamination. Develop and implement
procedures to deal with clean-up of CNT and CNF spills and de-contamination of surfaces.

Personal Protective Equipment

Working with nanomaterials the protection of the respiratory system is paramount. In 2008 research was
conducted on the effectiveness of N95 and P100 air purifying respirators. The study showed that the
NIOSH approved N95 and P100 air-purifying respirators provided expected levels of protection (Samy
Rengasamy, 2008).
For the protection of skin and hands Lab coats or regular textile work coveralls are protective
according to NIOSH. Gloves made of neoprene, nitrile and other chemical resistant gloves should be
worn and changed frequently or whenever they are visible worn, torn or contaminated.

Conclusion
The nanotechnologies are estimated to account for up to $4.0 trillion worth of manufactured goods by
2015, representing a compound annual growth rate of 41% (Lux Research, 2008). Some estimates project
2 million workers globally, with at least 800, 000 of these in the USA alone (Roco and Bainbridge, 2005).
The nanotechnologies find diverse use in high-performance intermediates, such as coatings and
composites for aerospace, automobiles, and construction, and in electronics, displays, batteries, and

healthcare. Nanomaterials are here to stay and with common sense and the application of well-known
engineering controls, they can be handled safely.

Bibliography
Ashley R, Murray, E.H. 2012. "Factoring-in agglomeration of carbon nanotubes and nanofibers for better
prediction of theirtoxicity versus asbestos." Particle and Fibre Toxicology 1-19.
Bello D, W. B. 2009. "Exposure to nanoscale particles and fibers during machining of hybrid advanced
composites containing carbon nanotubes." Journal of Nanoparticle Research 231-249.
E.R. Kisin, A. M.B. 2011. :Genotoxicity of carbon nanofibers: Are they potentially more or less
dangerous than carbon nanotubes or asbestos?" Toxicology and Applied Pharmacology 1-10.
Filtration Group Inc. (n.d.). "Filtration Group Inc." Retrieved March 13, 2012, from HEPA seal bag
in/bag out operation and maintenance manual:
www.filtrationgroup.com/../HEPA_BagIn_BagOut_Housing_Install_01.pdf
Gribbin, J., and Gribbin, M. 1997. Richard Feynman: A Life in Science. London, New York: Viking.
Kulinowski, K. M. 2014. "Introduction to Nanomaterials and Occupational Health." (Retrieved 3 3, 2014)
(https://nanohub.org/groups/gng/training_materials)
Murray AR, K. E. 2009. "Oxidative stress and inflammatory response in dermal toxicity ofsingle-walled
carbon nanotubes." Toxicology 161-171.
NIOSH Publications and Products. 2013. (Retrieved March 13, 2014)
(http://www.cdc.gov/niosh/docs/2014-102/)
Pauluhn, J. 2010. "Multi-walled carbon nanotubes (Baytubes): Approach for derivationof occupational
exposure limit." Regul Toxicol Pharmacol.
Samy Rengasamy, W. P. 2008. "Filtration Performance of NIOSH-Approved N95 and P100 Filtering
Facepiece Respirators Against 4 to 30 Nanometer-Size Nanoparticles." Journal of Occupational
and Environmental Hygiene 556-564.
Su-Jung (Candace) Tsai, E. A. 2009. "Airborne nanoparticle exposures associated with the manual
handling of nanoalumina and nanosilver in fume hoods." NANOPARTICLES AND
OCCUPATIONAL HEALTH 147-161.
United States National Nanotechnology Initiative (NNI). n.d. "Benefits and Applications." (Retrieved
March 10, 2014) (http://www.nano.gov/you/nanotechnology-benefits)
Wikipedia 2014. "HEPA." (Retrieved March 10, 2014) (http://en.wikipedia.org/wiki/HEPA)