Aasgeir HellandI; Peter WickII; Andreas KoehlerI; Kaspar SchmidIII; Claudia

SomI
Technology and Society Lab, EMPA (Swiss Federal Laboratories for Materials Testing
and Research), St. Gallen, Switzerland. Lerchenfeldstrasse 5, CH-9014 St. Gallen,
Switzerland. [email protected]
II
Laboratory for Biocompatible Materials, EMPA, St. Gallen, Switzerland
III
Institute for Occupational Health Sciences, Lausanne, Switzerland
I

ABSTRACT
Carbon nanotubes (CNTs) are one of the most promising materials in
nanotechnology. The various synthesis, purification and postprocessing methods
produce CNTs with diverse physical characteristics, appliable in many fields. Their
extensive projected use makes it important to understand their potential harmful
effects. Besides showing a notable range of results of some toxicology studies, this
review concluded that: a) there are different types of CNTs; thus, they cannot be
considered a uniform group of substances; and b) in environmental compartments,
CNTs can be bioavailable to organisms. Their properties suggest a possible
accumulation along the food chain and high persistence. In organisms, CNT
absorption, distribution, metabolism, excretion and toxicity depend on the inherent
physical and chemical characteristics (e.g., functionalization, coating, length and
agglomeration state), influenced by external environmental conditions during CNT
production, use, and disposal. Thus, characterized exposure scenarios could be
useful in toxicology studies. However, upon reaching the lungs in enough quantity,
CNTs produce a toxic response (time and dose-dependent). The risks to human
health and environment should be identified for a successful introduction of CNTs in
future applications.
Key words: Carbon nanotubes, Cytotoxicology, Environment, Human health,
Nanotechnology

RESUMO
Os nanotubos de carbono(CNT)so um dos materiais mais promissores da
nanotecnologia. Os mtodos de sntese, purificao e ps-processamento produzem
CNT com diversas caractersticas fsicas e uso em vrias reas. A projeo de uso
abrangente do CNT urge a compreenso de seus possveis efeitos nocivos. Essa
reviso mostra um leque de resultados de estudos toxicolgicos e concluiu que: a)
h diferentes tipos de CNT; portanto, no pode ser considerado um grupo uniforme
de substncias; e b) em compartimentos ambientais,o CNT pode ser biodisponvel
aos organismos. Suas propriedades sugerem possvel acmulo na cadeia alimentar
e alta persistncia. Em organismos, sua absoro, distribuio, metabolismo,
excreo e toxicidade do dependem de caractersticas fsicas e qumicas inerentes
(e.g., funcionalizao, revestimento, comprimento e estado de aglomerao),
influenciadas por condies ambientais externas durante a produo, uso e

eliminao de CNT. Portanto, os cenrios de exposio caracterizados podem ser

teis em estudos toxicolgicos. Contudo, quando chega aos pulmes em quantidade
suficiente, o CNT produz uma resposta txica (tempo e dose dependente). Os riscos
sade humana e meio ambiente devem ser identificados para que o CNT possa
ser usado com sucesso em futuras aplicaes.
Key words: Nanotubos de carbono, Citotoxicologia, Meio ambiente, Sade
humana, Nanotecnologia

The worldwide funding devoted to nanotechnology research and development by

governments, industry, and venture capitalists was estimated to be around US$9.6
billion in 20051. A large portion of this spending is still being allocated tothe
development of nanoparticulate materials because of their many novel physical and
chemical properties raising high expectations for a variety of applications. One of
these new materials is carbon nanotubes (CNTs), which have commercial
expectations in different manufacturing sectors.
However, epidemiologic studies of air pollution suggest that particulate matter has a
strong association with cardiopulmonary diseases2. Research has shown that
nanoparticles may enter the human body more easily and be more biologically
active because of their larger surface area per mass unit compared with that of
larger particles3. The prospective widespread use of engineered nanoparticles in
consumer products may increase environmental, occupational, and public
exposures dramatically. Consequently, different stakeholders have raised serious
concerns regarding health effects of engineered nanoparticles4. Recent review
articles on the toxicitypotential of nanoparticles5,3 conclude that the toxicity of
nanoparticles depends on specific physiochemical and environmental factors. Thus,
the toxic potential of each type of nanoparticle has to be evaluated individually.
Here we review the currently available literature on the potential risks of CNTs to
human health and the environment. We also investigated the life cycle of CNTs, as
release into different environmental compartments may occur at the production
stages as well as at the product's use and disposal stages, which may directly or
indirectly lead to human exposure.However, the published literature revealed many
unanswered questions. Therefore, we also systematically interviewed seven leading
world-class scientists and integrated their contemporary knowledge into this review
(see Supplemental Material;http://www.ehponline.org/docs/2007/9652/suppl.pdf).
This assisted us in identifying questions and developing recommendations. The
scientists interviewed were key authors or project leaders who have investigated
and reported the potential impacts of CNTs on human health or environment.
Through this combined approach we are able to present an updated and
contemporary knowledge base for scientific discussion.
In this review, we use the term "carbon nanotubes" when addressing the
generalaspects of the material, which includes singlewalled carbon nanotubes
(SWCNTs) and multiwalled carbon nanotubes (MWCNTs). Here "multi" is defined as
two or more walls. The terms "SWCNTs" and "MWCNTs" are used in a specified
manner.

Exposure to carbon nanotube material

Exposure in occupational settings
Procedures for the handling of CNTs can result in aerosol release of these materials
into the surroundings6. MWCNT aerosols generally have diameters between 20 nm
to > 200 nm, lengths from 1,000 nm to > 106 nm, and different shapes (straight,
partly rigid, bent, curled, and partly flexible) that may appear single or in clumps or
ropes7.
Only one published study has investigated the potential for SWCNTs to become
airborne. A laboratory study by Maynard et al.6 investigating the physical nature of
the aerosol formed during mechanical agitation was complemented by a field study
of SWCNT release during handling of unrefined SWCNTs. The authors found that
sufficient agitation of unrefined SWCNT material can release fine particles into the
air, but the concentrationsgenerated while handling the material in the field were
very low (< 53 g/m3). The laboratory study also revealed that different SWCNT
production methods produced different types of aerosols. The laser ablation process
generated a more compact aerosol that was difficult to break down into smaller
particles, whereas the HiPCO (high-pressure carbon monoxide) process generated a
more extended material that was easier to break down into smaller particles and
appeared to lead to higher airborne concentrations.
Maynard et al.6 also found glove deposits of SWCNTs during handling that were
estimated at between 0.2 and 6 mg per hand and thus concluded that large SWCNT
containing clumps had the propensity to become airborne and could remain so for
long periods. This may cause dermal exposure and health risks even in less wellprotected areas. Maynard et al.6 noted that production volume was very small
(research facility) and that workers took great care to reduce product loss during
handling of the material. However, CNTs contain catalyst metals such as nickel,
which is associated with increased risks of cancerin the nose region8.
Cleaning operations can also lead to emissions. The cleaning of the production
chambers is performed usually using solvents or water, tissues, brushes, and
sponges that are discarded after cleaning9. This waste carries CNTs into the waste
stream, thereby possibly becoming a source of release into the environment.
Exposure through environmental media
Exposure through environmental media is highly relevant for several reasons: a)
The widespread applications envisioned for CNTs may lead to substantial production
volumes, and consequently to increased emissions into the environmental
compartments air, groundwater, and soil. b) The physical and chemical processes in
the environmental compartments may alter the properties of CNTs, for example,
abiotic factors such as ultraviolet light may alter the coatings of CNTs as observed
with fullerenes10 and quantum dots11. Consequently, this may also change the
behavior of CNTs in the environment and thus influence their environmental fate
and impact. c) CNTs are possibly one of the least biodegradable man-made
materials ever devised12. They are totally insoluble in water in pristine form12 and
are lipophilic by nature13. It is generally known that biopersistent and lipophilic
chemicals may accumulate along the food chain; therefore, such a scenario should
also be evaluated with CNTs. In aqueous environments, SWCNTs clump together to
form aggregates in the micrometer range; these aggregates do not change in size
distribution with increasing salinity or temperature14. However, the aggregation
differs with pH changes in water14 and postsynthesis treatment of the SWCNTs with,
for example, acid or surfactants15. Both these studies found that pristine nanotubes

formed stable aggregates,whereas acid-treated nanotube suspension showed

greater dispersion variability over time, yielding looser structures at large-length
scales and more compact structures at small-length scales. The addition of a
surfactant to CNTs resulted in a hydrophilic interface at the tip of the nanotubes
that significantly enhanced nanotube dispersion. In laboratory assessments
designed to assess the potential migration innatural porous media, SWCNTs have
been shown to have mobility and deposition behaviors different from those of other
nanoparticles16, 17. SWCNTs functionalized to facilitate dispersion in water displayed
the highest mobility together with water-soluble fullerol, whereas colloidal C60,
anatase titanium dioxide (TiO2), and ferroxane were among the least mobile of the
nanomaterials evaluated.
The large surface area of CNTs may cause other molecules to adhere and potentially
pick up pollutants and transport these throughout the environment18. Several
studies have investigated different carbon nanomaterials as superior sorbents of
organic pollutants, metals, fluoride, and radionuclide 243-americium [243Am(III)] 1921
. Yang et al.21 found a high adsorption capacity of polycyclic aromatic
hydrocarbons (PAHs) with different types of CNTs (MW and SW). This finding
indicates a potential effect on the fate of PAHs upon their release into the
environment. The adsorption capacity was found with the order SWCNTs > MWCNTs
> C60 and seemed to be related tothe surface area, micropore volume, and the
volume ratios of mesopore to micropore.
Oberdrster et al.22, in a preliminary study, investigated the ingestion of SWCNTs
by the suspension-feeding worm Caenorhabditis elegans. SWCNTs moved
through the digestive tract and were not absorbed by the animal. However, even if
SWCNTs did stay in the digestive tract, these materials could move up the food
chain, as these worms and other organisms are consumed by benthivores. SWCNTs
have also been shown to be bioavailable to aquatic organisms, as both watersolubilized (wrapped with a synthetic peptide) and unsolubilized SWCNTs were
detected in the fecal material collected from the digestive tract in the exposed
fish23. For the water-solubilized SWCNT-exposed fish, clumps of SWCNTs were also
found on the gill, but similar clumps were not visible in unsolubilized SWCNTexposed fish. However, the fish mistook the unsolubilized SWCNTs (floating on top
of the water) for food and ingested them22. Furthermore, because pristine CNTs are
lipophilic, there is concern that they might be taken up by microbial communities
and roots22 and, consequently, accumulate in plant tissues.
Carbonaceous nanoparticles, including MWCNTs, can also be formed by natural
processes24 and anthropogenic combustion processes25. Although these MWCNTs
can be prime suspects in the pathogenesis of cardiopulmonary diseases induced by
fine particulate matter, there are physical differences between combustiongenerated and manufactured MWCNTs26. These MWCNT structures may therefore be
less important when the impacts of engineered CNTs are being assessed, as the
studies to date suggest that when the properties of CNTs are altered by
engineering, changes in the environmental fate of and human exposure to CNTs
occur through the different environmental media.