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Document 52012SC0288
COMMISSION STAFF WORKING PAPER Types and uses of nanomaterials, including safety aspects Accompanying the Communication from the Commission to the European Parliament, the Council and the European Economic and Social Committee on the Second Regulatory Review on Nanomaterials
COMMISSION STAFF WORKING PAPER Types and uses of nanomaterials, including safety aspects Accompanying the Communication from the Commission to the European Parliament, the Council and the European Economic and Social Committee on the Second Regulatory Review on Nanomaterials
COMMISSION STAFF WORKING PAPER Types and uses of nanomaterials, including safety aspects Accompanying the Communication from the Commission to the European Parliament, the Council and the European Economic and Social Committee on the Second Regulatory Review on Nanomaterials
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COMMISSION STAFF WORKING PAPER Types and uses of nanomaterials, including safety aspects Accompanying the Communication from the Commission to the European Parliament, the Council and the European Economic and Social Committee on the Second Regulatory Review on Nanomaterials /* SWD/2012/0288 final */
COMMISSION STAFF WORKING PAPER Types and uses of nanomaterials, including
safety aspects Accompanying the Communication from the Commission
to the European Parliament, the Council and the European Economic and Social
Committee on the Second Regulatory Review on
Nanomaterials 1. Introduction The European Parliament in its resolution
of 24 April 2009 on Regulatory Aspects of Nanomaterials[1] called
on the Commission to compile an inventory of nanomaterial types and uses. In
particular, it stated: “H. whereas there is no clear information
about the actual use of nanomaterials in consumer products, for instance: - while inventories by renowned
institutions list more than 800 manufacturer-identified nanotechnology-based
consumer products currently on the market, trade associations of the same
manufacturers question these figures, on the basis that they are overestimations,
without providing any concrete figures themselves, - while companies happily use
“nano-claims”, as the term “nano” seems to have a positive marketing effect,
they are strictly opposed to objective labelling requirements, J. whereas presentations about the
potential benefits of nanotechnologies predict an almost infinite diversity of
future applications of nanomaterials, but fail to provide reliable information
about current uses, 16. Calls on the Commission to compile
before June 2011 an inventory of the different types and uses of nanomaterials
on the European market, while respecting justified commercial secrets such as
recipes, and to make this inventory publicly available; furthermore calls on
the Commission to report on the safety of these nanomaterials at the same time” In its response[2] of 14 July
2009 the Commission stated in relation to paragraph 16 of the above resolution that
“the Commission intends to present information on types and uses of
nanomaterials, including safety aspects, in 2011.” This formulation was
chosen because at the time of the resolution the implications of an “inventory”
were unclear and required further analysis, including an analysis of
registration dossiers under the first registration deadline of the REACH
Regulation[3] and of notification dossiers under the CLP Regulation[4]. In its conclusions on “improving
environmental policy instruments” of 20 December 2010[5], the
Council invited the Commission to “evaluate the need for the development of
specific measures for nanomaterials relating to risk assessment and management,
information and monitoring, including the further development of a harmonized
database for nanomaterials, while considering potential impacts”. This Staff Working Paper intends to present
available information on types and uses of nanomaterials, including safety
aspects and to discuss options for a harmonised database for nanomaterials,
considering potential impacts. In principle, the Staff Working Paper
covers nanomaterials within the scope of Commission Recommendation 2011/696/EU on
the definition of nanomaterial.[6] Nevertheless, as the request by the European Parliament is related
to nanomaterials on the market, this document focuses on manufactured
nanomaterials, and does not cover naturally occurring nanomaterials (e.g. dust,
volcanic ash etc.) and incidental nanomaterials (e.g. particulate matter from
combustion installations). The current EU definition of nanomaterial
focuses on nanomaterials with a majority of particles in the nanoscale (1 nm to
100 nm). It is noted that particular varieties of many of the particulate
materials discussed in this Staff Working Paper may or may not fall under the
definition in Recommendation 2011/696/EU, depending on their specific particle
size distribution. For reasons of readability, the Staff Working Paper follows
the common practice in using terms for nanomaterials, i.e. when referring to
nano-titanium dioxide[7], the prefix “nano” is not always used, whereas it is used in other
cases such as “nanosilver”. However, any numbers such as production tonnages or
market values always refer to the total of all nanoforms on the market, unless
indicated otherwise. In chapters 2 to 5, the Staff Working Paper
intends to give further explanations on the EU definition of nanomaterial, give
an overview of the main types and uses of nanomaterials on the EU market, as
well as information on their safety, according to current knowledge available
to the Commission, and an overview of issues and activities relating to risk
assessment of nanomaterials. In principle, such information can be presented
from the perspective of substances at nanoscale, i.e. chemical substances as
defined under REACH which are nanomaterials or have forms which are
nanomaterials[8], enumerating their main uses through the supply chain and in final
products, or from the perspective of finished products or product areas. In
this document, the former approach has been chosen because the number of
substances at nanoscale is much more limited than the number of products
containing nanomaterials and it is therefore easier to present the information
in a structured manner. Information on uses in products can be found under each
substance heading. This document can, however, not give a
complete or exhaustive picture on all nanomaterial forms or variations of
substances. Nanomaterials are often tailored in a very specific way to achieve
desired properties. This may alter their behaviour as well as their
toxicological and ecotoxicological properties, throughout their life-cycles. In
considering the safety of individual forms or variations, care should therefore
be taken to properly take into account such variations in combination with
specific uses of a particular form, where resulting in different exposure
scenarios. In chapter 6, the Staff Working Paper
analyses existing databases on nanomaterials and gives information on a planned
European Commission web platform on nanomaterials types and uses, including
safety aspects. 2. Definition and types of nanomaterials The Commission adopted on 18 October 2011
Commission Recommendation 2011/696/EU on the definition of Nanomaterial.[9] The Recommendation responds to the increasing use of specific
legislative provisions addressing nanomaterials and the need to ensure
harmonised terminology across different pieces of legislation, as well as to a
request by the European Parliament.[10] The Recommendation is based on the ISO term
“nanomaterial”[11], a Reference Report of the European Commission’s Joint Research
Centre (JRC)[12], an opinion of the Scientific Committee on Emerging and Newly
Identified Health Risks (SCENIHR)[13], on
the 195 contributions received during public consultation[14] in October – November 2010, as well as on a number of other
sources. The advice is presented in more detail below in chapters 2.2 and 2.3. The core elements of the definition are
laid down in articles 2 to 4: “2. "Nanomaterial" means a
natural, incidental or manufactured material containing particles, in an
unbound state or as an aggregate or as an agglomerate and where, for 50 % or
more of the particles in the number size distribution, one or more external
dimensions is in the size range 1 nm - 100 nm. In specific cases and where warranted by
concerns for the environment, health, safety or competitiveness the number size
distribution threshold of 50 % may be replaced by a threshold between 1 and 50
%. 3. By derogation from point 2, fullerenes,
graphene flakes and single wall carbon nanotubes with one or more external
dimensions below 1 nm should be considered as nanomaterials. 4. For the purposes of point (2),
"particle", "agglomerate" and "aggregate" are
defined as follows: (a) "Particle" means a minute
piece of matter with defined physical boundaries; (b) "Agglomerate" means a
collection of weakly bound particles or aggregates where the resulting external
surface area is similar to the sum of the surface areas of the individual
components; (c) "Aggregate" means a particle
comprising of strongly bound or fused particles.” The purpose of the Recommendation is to
ensure consistency across legislative areas as well as across guidance and
other technical documents by the European Commission. In
addition, the Commission invites Member States, the Union agencies and economic
operators to use this definition, for example, in the adoption and
implementation of legislation and policy and research programmes concerning
products of nanotechnologies 2.1. Application in legislation The definition will primarily be used in
future legislation or in updates of existing legislation to identify materials
for which special provisions (concerning for example risk assessment or
ingredient labelling) might apply. Those special provisions are not part of the
definition but of specific legislation in which the definition will be used. The
Recommendation offers a common understanding of the term “nanomaterial” to
avoid confusion on terminology and inconsistency between different pieces of
legislation. This does not mean that specific legislation needs to apply to all
nanomaterials, or that there could not be legislation covering similar
materials outside the definition. Since the definition is broad in its
coverage, further sector specific qualifiers may be needed in order to identify
more precisely those materials that should potentially be subject to specific
legislative requirements or policy attention. For example it is likely that in many cases
only materials that are a designed product of a deliberate manufacturing
process will be of interest (commonly referred to as "engineered" or
"manufactured" nanomaterials). Thus further qualifiers may be added
on a case-by-case basis, in order to target the specific materials that qualify
for special attention within each regulatory sector. Another consideration is that in certain
specific sectors, like pharmaceuticals, it is established practice to refer to
nanoscale being broader than 1 nm – 100 nm. The Recommendation clearly
specifies that in such a situation other "nano"-terms may be needed
to describe those products. 2.2. Reference Report of the
Joint Research Centre In June 2010 the Joint Research Centre of
the European Commission released its Reference Report 'Considerations on a
Definition of Nanomaterial for Regulatory Purposes'.[15] The
aim of this report was to review and discuss issues and challenges related to a
definition of ‘nanomaterial’, and to provide practical guidance for a
definition for regulatory purposes. The report suggests that a definition for
regulatory purposes should: ·
only concern particulate nanomaterials, ·
be broadly applicable in EU legislation, and in
line with other approaches worldwide, ·
use size as the only defining property. 2.3. The SCENIHR opinion The Commission also invited the Scientific
Committee on Emerging and Newly Identified Health Risks (SCENIHR) to provide
scientific input on elements to consider when developing a definition of the
term "nanomaterial" for regulatory purposes. The opinion
"Scientific basis for the definition of the term 'Nanomaterial" was
adopted on 8 December 2010.[16] SCENIHR concluded that: ·
"Whereas physical and chemical properties
of materials may change with size, there is no scientific justification for a
single upper and lower size limit associated with these changes that can be
applied to adequately define all nanomaterials. ·
There is scientific evidence that no single
methodology (or group of tests) can be applied to all nanomaterials. ·
Size is universally applicable to define all
nanomaterials and is the most suitable measurand. Moreover, an understanding of
the size distribution of a nanomaterial is essential and the number size
distribution is the most relevant consideration. In order to define an enforceable
definition of “nanomaterial” for regulatory use it is proposed to set an upper
limit for nanomaterial size and to add to the proposed limit additional
guidance (requirements) specific for the intended regulation. Crucial in the
guidance that needs to be provided is the extended description of relevant
criteria to characterise the nanoscale. Merely defining single upper and lower
cut-off limits is not sufficient in view of the size distributions occurring in
manufactured nanomaterials. Alternatively, a tiered approach may be
required depending on the amount of information known for any specifically
manufactured nanomaterial and its proposed use. The scientific opinion recognises however
that specific circumstances regarding risk assessment for regulatory purposes
for certain areas and applications may require the adaptation of any
overarching definition. It should be stressed that 'nanomaterial'
is a categorization of a material by the size of its constituent parts. It
neither implies a specific risk, nor does it necessarily mean that this material actually has new hazard properties compared to its
constituent parts or larger sized counterparts." 2.4. The international context Several countries, both inside and outside
the EU have developed and use working definitions. All these have been
carefully scrutinised. There is variability between the different working
definitions but most of them are not as precise as the Commission
Recommendation. Most non-EU countries generally use their definitions in a
different regulatory context mainly to identify individual materials and/or
uses, which then may be subject to specific data provision or risk assessment
obligations. In the EU, provisions in individual pieces of legislation (e.g.
ingredient labelling, prior notification and authorisation etc.) apply directly
to all producers of products containing nanomaterials. Therefore, much more
precision is required to provide legal clarity. Several international organisations have
developed their definition of the term nanomaterial. Among these, the
definition released by ISO in 2010 (in ISO/TS 80004-1) was developed with the
broadest stakeholder base. The approved definition ('material with any external
dimension in the nanoscale (2.1) or having internal structure or surface
structure in the nanoscale') is fundamentally based on the term 'nanoscale'
which was previously defined by ISO (in 2008 in ISO/TS 27687) as 'the size
range from approximately 1 nm to 100 nm'. The ISO definition is used as a working
definition for example by the OECD Working Party on Manufactured Nanomaterials
(OECD-WPMN). Whilst this broad working definition has proved useful for
progressing research and development in this field, it could not be directly
used for legal texts, for example due to the approximate nature of the term nanoscale. 2.5. Essential elements of the
definition 2.5.1. The size range 1 nm – 100 nm There is no clear scientific justification
for setting the thresholds at 1 nm and 100 nm, as specific effects
may also occur at a lower and higher size range. On the other hand, particles
within the size range of 1 nm to 100 nm may also not show a specific
behaviour different from the behaviour of larger particles of the same
material. Nevertheless, many of the described specific properties of
nanomaterials are actually generated by physics and chemistry within that range.[17] Therefore, in the absence of better arguments for other thresholds,
the Commission decided to follow the approach most commonly applied to date,
i.e. a size range between 1 nm and 100 nm. This is in line with the
advice from SCENIHR and other scientific bodies, as well as with the size range
used in the ISO term “nanomaterial”. To make the definition useful for
regulatory purposes, it was chosen not to retain the term 'approximately',
which qualifies the 1 nm to 100 nm range in the ISO definition. 2.5.2. Aggregates and agglomerates To some extent, agglomerated or aggregated
particles may exhibit the same properties as unbound particles and are
therefore covered by the definition. Moreover, there can be cases during the life-cycle
of a nanomaterial where the particles are released from weakly bound
agglomerates or under certain conditions even from more strongly bound
aggregates. The definition in the Recommendation therefore includes particles
in agglomerates or aggregates whenever the constituent particles are in the
size range 1 nm - 100 nm. 2.5.3. Based on number of
particles, not mass The amount of nanoparticles in a material
can be determined based on their mass fraction (weight of nanoparticles relative
to total weight of material) or based on the particle number fractions (number
of nanoparticles to total number of particles, "number size
distribution"). Most measurement methods produce an intensity-weighted
size distribution (expressing the fractions of particles of a particular size
as their relative contribution to the total measured signal intensity). There
is a relation between these different size distributions, for every material,
but these relations are not usually known and the different size distributions are
therefore not directly convertible. SCENIHR argued in its opinion that "a
low mass concentration of nanoparticles in a product may still represent a high
number of particles and a mass based distribution can be skewed by the presence
of relatively few large and thus heavy particles". As the smallest
particles have a proportionally higher specific surface area, which may be
relevant for toxicity properties, SCENIHR considered number size distribution
as a more relevant metric for possible effects of nanoparticles. The Commission followed this choice of
metrics. Further work is certainly needed on the metrological and
standardisation aspects. Previous efforts, for example in the field of fine
dust (PM10, PM2.5, etc.), are naturally extending now
into the nanoscale. The Commission has already started work to provide
practical guidance on particle size measurement methods[18],[19] and quality assurance tools such as interlaboratory studies,[20],[21] nanoparticle reference materials[22],[23],[24] for particle size analysis (see also Appendix 9 for further detail),
and characterization of complex mixtures of nanoparticles.[25] 2.5.4. A threshold in the number
size distribution There is no unequivocal scientific basis to
suggest a specific threshold in the size distribution below which materials
containing particles in the size range 1 nm – 100 nm are not expected
to exhibit properties specific to nanomaterials. Because of the proportionally
higher specific surface area which may be relevant for toxicity properties exhibited
by the smallest particles, and following a classic scientific approach to
consider three standard deviations, the SCENIHR's advice was to use a threshold
value of 0.15 %. The Commission decided to deviate from this
threshold value based on several considerations. Nanoparticles are present in
low quantities in most solid materials. The percentage may be significant, in
particular in certain powders. Therefore, a threshold of 0.15 % could
include too broad a range of materials within the definition, and would have
made it difficult to tailor regulatory provisions appropriately. Nevertheless, in accordance with SCENIHR's
advice, even a small number of particles in the range between 1 nm – 100 nm
may in certain cases justify a targeted assessment. For such cases, the Recommendation
clearly specifies that where warranted by specific concerns for the
environment, health, safety or competitiveness a threshold between 1 % and
50 % may be set. These threshold values will be subject to further review
by 2014. 2.5.5. The Volume specific surface
area It is possible to measure a specific
surface area by mass for dry solid materials or powders with the gas adsorption
method (“BET-method”). If the particle density is also known, then the
'volume-specific surface area' can be calculated and used as a proxy to
identify a potential nanomaterial. For some materials, there can be a
discrepancy between the measurement of the specific surface area and the number
size distribution. The measurement of the specific surface area is also
sensitive to the measurement method used. It is therefore specified that the
results for number size distribution should prevail and it should not be
possible to use the specific surface area to demonstrate that a material is not
a nanomaterial. 2.5.6. Practical use of the
definition Guidance and standardised measurement
methods as well as knowledge about typical concentrations of nanoparticles in
representative sets of materials should be developed where feasible and
reliable to facilitate the application of the definition in a specific
legislative context. The Commission will address these aspects as a matter of
priority. However, the use of the definition should not await the outcome of
this work and a pragmatic case-by-case approach needs to be applied for the
time being. In fact, this should be an iterative process where practical
experience will form an important aspect of the further development of measurement
methods and standards. 2.5.7. Review of the definition Some methodological issues and questions of
scope could not be fully answered in the preparatory work for the definition.
Moreover the nanotechnology sector is rapidly developing and it is therefore
expected that the market developments will require the Commission
Recommendation to be reviewed at certain intervals. The Recommendation will be
reviewed by December 2014. In view of this review, the Commission
services continue to follow up wider work on terms related to nanotechnology
and nanomaterials, for example by the International Organization for Standardization
(ISO). Details about this work and its relation with the current EU definition
are presented in Appendix 1. More information about standardisation work in
relation to nanomaterials is given in Appendix 9. 3. Overview of nanomaterials, their markets,
uses and benefits Nanomaterials cover a heterogeneous range
of materials. In terms of market volume the main categories on the market
include inorganic non-metallic nanomaterials (e.g. synthetic amorphous silica,
aluminium oxide, titanium dioxide), carbon based nanomaterials (e.g. carbon
black, carbon nanotubes), metal nanoparticles (e.g. nanosilver) and organic,
macromolecular or polymeric particulate materials (e.g. dendrimers). Nanomaterials
often exist in a variety of forms and may be tailored for individual properties
or uses. It was not possible to give market information at such a level of
detail, as this information is, if at all, not readily available. In terms of industrial impact and public
exposure the above-mentioned nanomaterials are of immediate regulatory
relevance. However, there are also new types of nanomaterials in development,
which are often referred to as “second generation” (targeted drug delivery systems, adaptive
structures and actuators), “third generation” (novel robotic devices,
three-dimensional networks and guided assemblies), and “fourth generation”
(molecule-by-molecule design and self-assembly capabilities) nanomaterials.[26],[27],[28] However, those are either at
research or development stage or at an early stage of market development. Due
to the limited available information on those materials, they are not further
considered in this Staff Working Paper. Any estimates of the market size need to be
taken with a certain degree of caution, although the general patterns of the
estimates (i.e. order of magnitude of tonnage and market value, and relative
size of market between the various materials) seem to be rather reliable.
According to market data from SRI consulting the global quantity of
nanomaterials marketed annually is around 11.5 million tonnes, with a market
value of roughly 20 bn €.[29] The market is dominated by two very widespread commodity materials,
i.e. carbon black (9.6 million t), and synthethic amorphous silica (1.5
million t). Other nanomaterials with significant amounts on the market include
aluminium oxide (200 000 t), barium titanate (15 000 t), titanium
dioxide (10 000 t [30]), cerium oxide (10 000 t), and zinc oxide (8 000 t).
Carbon nanotubes and carbon nanofibres are currently marketed at annual quantities
of several hundreds of tonnes (other estimates go up to a few thousands of
tonnes). Nanosilver is estimated to be marketed in annual quantities of around
20 tonnes. In addition, there is a wide variety of nanomaterials which are
either still at the research and development stage, or which are marketed only
in small quantities, mostly for technical and biomedical applications. The uses of nanomaterials vary
substantially, from commodity applications in everyday goods to highly
specialised low-volume technical applications, e.g. in electronics or
biomedicine. By far the biggest use is as a reinforcing agent for rubber in
tyres and other rubber goods (global market around 15 bn €, mainly carbon black),
followed by functional fillers in polymers (around 1.5 bn €, mainly synthetic
amorphous silica, in lower quantities also other metal oxides and silver),
various uses in electronics (1 bn €), in cosmetics (100 m €) and biomedical applications
(60 m €). In electronics, the biggest use are CMP[31]
slurries, i.e. fine abrasives (mainly colloidal synthetic amorphous silica)
used in the preparation of electronic components, followed by multi-layered
ceramic capacitors (MLCC, mainly barium titanate). In cosmetics, the main
nanomaterials are synthetic amorphous silica, titanium dioxide and zinc oxide.
Among biomedical applications, gold nanoparticles in medical diagnostics and silver
nanoparticles (e.g. in hospital textiles) seem to be the biggest applications
in terms of market value. In addition to those applications, there is use of a
wide range of nanomaterials in paints and coatings, catalysts, solar and fuel
cells, etc. The economic sectors with the highest use of
nanomaterials[32] are aerospace (e.g. lightweight materials,
resistant paints and coatings for aerodynamic surfaces); automotive industry and
transport (e.g. scratch-resistant paints and coatings, plastics, lubricants,
fluids, tyres); agrifood (e.g. sensors to optimise food production); construction
(e.g. insulation, stronger building materials, self-cleaning windows); energy generation (e.g. photovoltaics) and storage (e.g. fuel cells
and batteries); environment (e.g.
soil and groundwater remediation); cosmetics (e.g.
sunscreens, tooth paste, face creams); health, medicine and nanobiotechnology (e.g. targeted drug delivery); information
and communication technologies, electronics and photonics (e.g. semiconductor
chips, new storage devices and displays); security (e.g. sensors to detect
biological threats); and textiles (e.g. protective clothing, stronger,
self-cleaning or fire resistant fibres). The benefits of nanomaterials are as
diverse as the nanomaterials and their uses. They range from saving lives (e.g.
targeted cancer drug delivery) to major technological breakthroughs enabling
new applications or reducing the environmental impact of our society (e.g.
photovoltaic cells and batteries, light-weight high-strength materials), to improving
the function of everyday commodity products (e.g. carbon black in tyres,
synthetic amorphous silica in polymers, or as food or cosmetics additive) and
to improvements which are mainly of convenience nature (e.g. anti-odour socks).
Nanotechnology has been identified as a key
enabling technology (KET) by the High Level Expert Group (HLG) on Key Enabling
Technologies.[33] It is highly innovative and provides the basis for further
innovation and new products in a wide range of industries, as mentioned above.[34] Products underpinned by nanotechnology are forecast to grow from a
volume of 200 bn € in 2009 to 2 trn € by 2015.[35] These
applications will be essential for the competitiveness of a wide area of EU
products in the global market. There are also many newly founded SMEs and
spin-off companies in this high technology area. Currently, the direct
employment in nanotechnology is estimated at around 300000 to 400000 jobs in the
EU.[36] In many areas, nanomaterials can
significantly contribute to mastering the challenges of the future and the
objectives of the EU 2020 Strategy, such as smart growth, developing an economy
based on knowledge and innovation, and sustainable growth, promoting a
low-carbon, resource-efficient and competitive economy. They can provide
essential contributions to green technologies and environmental protection
(e.g. sensors for smart electricity grids, filters for drinking water). They
can also contribute to inclusive growth by providing new employment and keeping
jobs in the EU. It is difficult to find reliable
information on the relative strength of the EU in nanotechnology compared to
other regions of the world. The work on this document, in particular Appendix 2,
shows that manufacturers and users of nanomaterials are spread all over the
industrialised world. Among them are major companies that are located in the
EU. The KET HLG report mentions that the EU accounts for 27% of world wide
public funding on nanomaterials, 17% of patents[37], and 15%
of nano-based products.[38] To an extent, this may be influenced by the ongoing debate in the
EU on regulating nanomaterials. According to a recent survey[39], half of the manufacturers and importers of nanomaterials in Europe
replying to the survey considered the regulatory uncertainties the most
important challenge in bringing nanomaterials on the market. The emerging
economies such as the BRIC[40] countries are still behind the industrialised countries in terms of
production and uptake of nanomaterials but are quickly progressing. 4. Health and safety aspects Health and safety aspects include possible
intrinsic hazard patterns of the nanomaterials, exposure to workers, consumers
and at the waste stage, as well as applicable risk management measures. Hazards
are determined by the properties of the material itself.[41]
However, these hazards will only lead to health or environmental risks[42]if parts of the human body or the environment are exposed to doses
of the nanomaterial which can create harmful effects. Correspondingly, risks
are determined by a combination of hazards and the probability of exposure. 4.1. Hazard patterns The hazard patterns vary largely between
different nanomaterials. In its opinion of 19 January 2009[43], the Scientific Committee on Emerging and Newly Identified Health
Risks (SCENIHR) concluded: “The health and environmental hazards were
demonstrated for a variety of manufactured nanomaterials. The identified
hazards indicate potential toxic effects of nanomaterials for man and
environment. However, it should be noted that not all nanomaterials induce
toxic effects. Arguably, some manufactured nanomaterials have been in use for a
long time (carbon black, TiO2) and show low toxicity. The hypothesis
that smaller means more reactive and thus more toxic cannot be substantiated by
the published data. In this respect nanomaterials are similar to normal
substances in that some may be toxic and some may not. As there is not yet a
generally applicable paradigm for nanomaterial hazard identification, a case by
case approach for the risk assessment of nanomaterials is recommended.” In their recent joint report "Impact of Engineered Nanomaterials on Health: Considerations for
Benefit-Risk Assessment" EASAC[44] and
the European Commission's Joint Research Centre conclude that "there is only a limited amount of scientific evidence to suggest
that nanomaterials present a risk for human health".[45] Nanomaterials may have a wide range of
potential toxic effects, depending on their chemical nature, particle size
distribution, particle shape, surface state (e.g. surface area, surface
functionalisation, surface treatment), state of aggregation/agglomeration etc. Some
of the main known effects from experimental studies are described below and in
Appendix 2, under the relevant substance heading. Under experimental conditions,
the most common effects observed are a potential to cause oxidative stress and,
for some, inflammatory responses or even genotoxic effects. Like for all chemicals, the potential
harmful effects of nanomaterials depend on the doses to which human beings or
the environment are exposed to. Typically, experimental data are generated with
high doses, identifying effects, and subsequently determining no-effect levels.
At low doses, most nanomaterials show little effects in these experiments. Views
on whether nanomaterials are hazardous or pose risks diverge, as they depend
crucially on whether the experimental data are considered representative for
real life conditions.[46] Some consider that high dose experiments are a normal way of
identifying hazards and their results should be an indication of potential
risks, whereas others consider that experiments with such high doses are
unrealistic and that similar effects could be found at those doses even with
very common, non-hazardous substances. Moreover, the route and the conditions
under which test animals are exposed to nanomaterials is also critical and subject to substantial methological discussions.[47] There is however, a consensus on the
principle that hazards and risks differ significantly between nanomaterials and
that some are hazardous and others are not. For example, the joint EASAC-JRC report considers
that “Overload conditions especially in the lung (macrophages) have been
described for 20 years. It is now well known that overloading the lung with
dust particles will severely influence (reduce) the clearance process, thereby
prolonging dramatically the biological lifetime of particles within the lung.
Eventually, this leads to persistent inflammatory effects with all the
characteristics of lung diseases which often end in tumour formation.
Therefore, it is recommended that overload conditions should be avoided both in
animal studies and for in vitro experiments otherwise excessive doses will
generate false-positive results. This sense of realism is equally
warranted for intended applications where engineered nanomaterials are targeted
to the individual in relatively precise amounts. Moreover, testing genotoxicity
with overloading concentrations (often cytotoxic concentrations) is also
unrealistic as dying cells (apoptosis as well as necrosis) cleave their own
DNA, resulting again in false-positive effects[48]. If non-overload conditions are chosen, no carcinogenic effects for
such dust particles are found[49]."[50] There are little epidemiological data,
directly evaluating effects of nanomaterials under real life conditions. The
few available studies, e.g. on carbon black, are considered as inconclusive
because of inconsistent epidemiological evidence.[51] Some other nanomaterials such as synthetic amorphous silica have
been on the market for a considerable time, including in high exposure
conditions, with little, if any, known adverse health or environmental effects.
However, there is also an ever growing variety of new uses and modified forms,
for which such experience does not exist. Until
understanding is available on the impacts of different forms and modifications
of nanomaterials on the hazard patterns, particular care should be taken to
avoid undue generalisation of data from one form to another. In its 2006[52], 2007[53] and 2009[54] opinions, the SCENIHR acknowledged the possibility that
translocation of nanoparticles away from the portal of entry may occur in
humans and other species, and that the passage of nanoparticles across
membranes could give rise to adverse effects, for example within the
cardiovascular system or following passage across the blood – brain barrier. A number of in-vivo studies in rats
have demonstrated that certain nanomaterials can
penetrate into the body and reach certain organs and tissues (for example in the
lung, liver, kidneys, heart, reproductive organs, foetus, brain, spleen,
skeleton and soft tissues) via several routes (following inhalation, crossing
the pulmonary epithelium and entering the blood stream; or reaching the brain via
the olfactory nerve; or crossing the intestinal epithelium after ingestion).[55],[56],[57],[58],[59],[60],[61],[62],[63],[64] Moreover, there are open questions on bioaccumulation of
nanomaterials and elimination mechanisms from cells and organs. In animal studies, a whole series of
effects have been observed under experimental conditions with high doses (for
methodological discussions around such tests, see above). The most important
effects have been found in the lungs: there is evidence of inflammation, tissue
damage, oxidative stress, chronic toxicity, cytotoxicity, fibrosis, tumours.[65] Tumour formation was found in rat lungs following intraperitoneal
introduction of certain nanomaterials. Furthermore, in long-term studies with
intratracheal instillation with nanostructured carbon black, aluminium oxide,
aluminium silicate, titanium dioxide (hydrophilic and hydrophobic) and
amorphous silicon dioxide, tumours were induced by all of them[66],[67],[68],[69],[70]. Effects like inflammation, fibrosis and tumours were induced by
several granular nanomaterials in the lungs after respiratory exposure. Some
nanomaterials, including carbon black and titanium dioxide, were on the basis
of experimental animal studies classified as “possibly carcinogen to humans”
(group 2B) by IARC.[71] In particular, carbon nanotubes (CNTs) of length,
diameter and rigidity ratios comparable to those of toxic forms of asbestos were
shown to have a potential under experimental conditions to induce effects
similar to those of asbestos.[72] There is no clear evidence of acute effects in other organs than
lungs but chronic exposure may lead to elevated accumulation of translocated
nanomaterials eventually leading to adverse health effects.[73],[74],[75],[76],[77] In particular, in case of respiratory exposure to nanomaterials
special attention is to be given to the cardio-vascular system as natural
ambient particles and incidental ultrafine particles (e.g. welding fumes and
combustion products) show some similarities (poor solubility, persistence in
the lungs) that might indicate some common properties. [78],[79],[80],[81],[82],[83] Extensive data[84] on
adverse effects of particles of different sizes in ambient and indoor air can
also contribute to the understanding of the safety aspects of nanomaterials in
certain circumstances, in particular epidemiological and toxicological studies
addressing ultrafine particles.[85],[86],[87] Ultrafine particles are present in our everyday lives and at
various conventional workplaces, generated by the applied work processes (i.e.
work processes generating ultrafine dust, aerosols or fumes, such as spraying,
dry-cutting, polishing, material processing with laser applications, combustion
processes, welding processes generating metal-welding fumes, etc.).[88],[89],[90] Diesel exhaust exposure and PM10 concentrations have been related
to higher mortality in the general population at higher pollution rates, and to
aggravation of asthma and lung cancer in workers.[91] Fine particulate
matter exposures have also been linked to cardiovascular effects.[92],[93] Metal oxide fumes, for example by welding, casting and abrasive
treatment, may lead to metal fume fever and more severe irreversible
respiratory illness.[94] There are continuous gaps in knowledge in relation to health
effects of individual components of particulate matter.[95] There
is major ongoing research on the health impact of particulate matter, including
in particular transport-related particles, on human health.[96] A significant body of EU environmental
regulation including emission standards[97] and workplace
codes of practice or regulations have been designed to limit exposure to
particulate matter.[98] Catalytic effects and the risk of fire or
explosion should be taken into account in the risk assessment of handling powders
consisting of nanomaterials (nanopowders), in
particular metal nanopowders.[99] There is a number of experimental studies
on ecotoxicity of nanomaterials which show varying results and a variety of
ecotoxic effects. For example Zhu et al[100]
report reduced length and body weights of fish as a result of exposure to
fullerene aggregates. Silver and copper nanoparticles are known to be strongly
ecotoxic. There are indications that this is primarily related to ion release
(which is relatively high compared to bigger particles due to the larger
specific surface) rather than to the particles themselves. There are also many
studies on titanium dioxide and zinc oxide, showing diverging results,
depending on the forms of nanoparticles studied.[101]
Unfortunately, those forms were often inadequately characterized to enable the
results from these studies to be extrapolated to other circumstances. Overall,
the level of ecotoxicological knowledge is significantly lower than the level
of toxicological knowledge. There are many uncertainties relating to simulation
of environmental conditions in experiments (usually much higher concentration
and more short-term exposure than realistic environmental conditions,
interferences through solvents, strong dependence on forms of nanoparticles,
surface treatment etc.). There are also open questions
on bioaccumulation and long term exposure, even though this does not seem to be
a general issue for all nanomaterials, as shown by the long presence of certain
nanomaterials on the market, and the absence of observed effects for these
nanomaterials. Although it is not always possible to
identify which information in REACH registration dossiers relates to or covers
the nanoform(s), it should be noted that most of the substances registered
under REACH which have nanoforms have not been classified by the registrants
for any hazard endpoint.[102] In conclusion, toxicological
knowledge about nanomaterials is improving continuously. Despite the open
questions described above, available toxicological knowledge on nanomaterials
suggests that many nanomaterials are non-hazardous at moderate doses while
others are hazardous. There is a need for a more focused risk assessment of
nanomaterials, on a case-by-case basis. This should allow indentifying risks
related to specific nanomaterials and their uses, and taking appropriate risk
management measures. In the absence of more detailed knowledge, there is a need
to apply precautionary considerations to reduce exposure, in particular at the workplace.
Workplace exposure should be reduced to the minimum applying the hierarchy of
control measures according to the workplace legislation such as Directive
98/24/EC and specific guidance from the OECD (see 4.2). and, where these would
not be possible because of insufficient scientific information for the
necessary hazard and/or risk characterisation, applying the ALARA[103] principle on the workplace exposure to ensure the safe use of
nanomaterials in other ways. Moreover, this also does not preclude that additional
precautionary action such as substance or use restrictions for individual
substances (including on particular forms or modifications of nanomaterials) may
become necessary if new information becomes available indicating serious
potential risks. Scientific work to inform the risk assessments process should continue,
especially regarding nanomaterials for which initial information suggests
possible serious hazards, and for developing a better understanding of the role
of different forms and modifications of nanomaterials in generating specific
hazard patterns. 4.2. Exposure patterns There are very few measured data on
exposure to nanomaterials and available exposure models. Therefore, exposure
aspects can be mainly addressed through general considerations and assumptions
in exposure scenarios. One known important factor to characterise exposure is
whether nanoparticles occur as free particles, whether they occur in aggregates
or agglomerates, whether they are bound in a matrix or enclosed in equipment,
or whether they are transformed during the production process in a way that
they do not occur as nanoparticles in the finished product. Exposure is likely to be most serious if
particles occur in free form, although this seems to be relatively rare. Often,
nanoparticles aggregate or agglomerate under normal environmental conditions,
thereby changing (but not necessarily losing) their nanospecific properties. Studies
are investigating whether, once inhaled and in lung fluid, such aggregates/agglomerates
could de-aggregate/de-agglomerate and nanoparticles could be released.[104],[105] There can be cases during the life-cycle of a nanomaterial where
the particles are released from weakly bound agglomerates or under certain,
perhaps rather unlikely, conditions even from more strongly bound aggregates.
Exposure is less likely if nanomaterials are bound in a matrix or enclosed in
equipment. It may still occur in the long term, through environmental
degradation or at the waste stage, or during specific operations such as
abrasion or machining of the matrix. This may also have impacts on the
environment and indirectly on humans (e.g. through drinking water or air),
though the evidence is still very limited and controversial.[106],[107]Generally, the highest risk of exposure to nanomaterials is to
workers at the production stage, although this is also where exposure is
generally best controlled with the use of closed systems.[108] Nevertheless, risks of exposure during maintenance and cleaning of
such closed systems, as well as in the case of leakage have to be considered. Measurements
of airborne nanomaterials have shown higher levels where processes such as
extrusion and cutting of bags containing nanomaterials, or dry-sawing of
nanomaterial-containing composites took place.[109] The risk
of chronic exposure of workers to situations where such
nanomaterials-containing products are processed (e.g. polishing) requires
further investigation. Although there are very little measured
data, it seems quite obvious that exposure at the use stage varies strongly,
depending on the type of application. In technical applications where the
nanomaterials are bound in a matrix (e.g. paints or construction materials) or
embedded in equipment parts (e.g. in electronics), exposure during use is
estimated to be relatively low. Exceptions might be when such matrices are for
example abraded or machined (e.g. dry-sawed).[110] In
general, little or no information is currently available in the Safety Data
Sheets (SDS)[111],[112],[113],[114], making it often difficult for employers and workers at the use
stage to assess specific exposure to nanomaterials and to implement adequate
prevention measures. Relevant changes in REACH Annex II, which is the legal
framework for Safety Data Sheets, have been made recently[115], and the recent guidance from ECHA on the Safety Data Sheets gives
further advice on how to address characteristics of nanomaterials.[116] There are ongoing discussions whether leaching (e.g. of outdoor
paints or release at the end-of-life) could lead to the release of significant
amounts of nanoparticles. In other applications such as in food and cosmetics,
exposure is estimated to be high due to ingestion or direct contact with the
skin. In between there are applications such as tyres, where a certain degree
of wear and thus environmental exposure occurs. Exposure to nanomaterials may also occur at
the waste stage. Although still controversial and subject to debate, there are
results from studies on grinding of materials consisting of nanomaterials bound
in a common matrix[117] which do not confirm that those nanoparticles are released from the
matrix during grinding (like in any fine grinding process, there can be release
of nanoparticles but these are also formed in a similar way from the matrix in
which the bound nanoparticles are embedded or from matrices which do not
contain any nanomaterials at all). However, fine airborne particles containing
manufactured nanoparticles could be inhaled and thus could possibly serve as a
“vehicle” transporting nanomaterials into the body. Studies are investigating
whether, once in the body, such bound nanomaterials could be released (for
example in lung fluid) or would influence the toxicity of the fine particles.[118],[119] There are few studies on the environmental
fate and behaviour of nanomaterials. This is mainly due to a lack of methods to
detect nanoparticles in the environment. A particular problem is the
distinction between manufactured nanoparticles and incidental or natural
nanoparticles. Even under workplace conditions, the background level in
airborne nanoparticles (e.g. through diesel exhaust nanoparticles) may dominate
over additions through emissions from the manufacturing process. Apart from
clear indications that nanoparticles interact with natural organic matter,
there is also little information about the fate of nanoparticles in the aquatic
environment. In addition, there may also be exposure to
nanomaterials as a result of their presence in recycled materials. While there
is no information available on any identified adverse effects to date, the
issue is starting to be considered.[120],[121],[122] In conclusion, much more work on developing
exposure data and detection methods for nanomaterials in the environment is
needed. 4.3. Risk characterisation Mainly as a result of the lack of exposure
data[123], risk characterisation and combining hazard and exposure data
necessarily remains at a very preliminary and qualitative level. As long as the
considered nanomaterials are non-hazardous and do not bio-accumulate, this is a
limited problem, as exposure to such materials is unlikely to cause toxic and
ecotoxic effects, at least at moderate doses. Where exposure is unlikely to
occur, either because nanomaterials are strictly contained or embedded in a
matrix, or as a result of risk management measures, this will also be a limited
problem. Therefore, the focus of attention of the regulators should be those
nanomaterials for which initial information suggests possible hazards or
bioaccumulation and the applications of these nanomaterials where significant exposure
of workers, consumers or the environment may occur. According to current knowledge, examples of
such nanomaterials are the different forms of nano-titanium
dioxide and nano-zinc oxide (due to high potential exposure, in particular in
their applications as UV-filters), carbon nanotubes (for the possible
carcinogenicity of certain forms) and nano-silver (for possible ecotoxicity). However, priorities will need to be
reviewed depending on the outcome of this work and on new scientific and market
developments. In particular in emerging uses, hazard patterns of nanomaterials
may be different from studied forms, including through modification by
downstream users of nanomaterials. Exposure patterns of nanomaterials may change
with their uptake in specific new applications. Therefore, care must be taken
that those trends are adequately reflected in risk assessments, including
exposure scenarios. 4.4. Risk management There is a variety of possible risk
management measures to avoid exposure, in particular at the workplace. Prevention
of occupational risks is an employer’s responsibility according to Directive
89/391/EEC on the introduction of measures to encourage improvements in the
safety and health of workers at work.[124] In
situations where elimination of the risk or substitution by a substance less
hazardous are not possible, the hierarchy of control measures as provided for
by Directive 98/24/EC on the protection of the health and safety of
workers from the risks related to chemical agents at work[125] gives priority to reduction of the risk at source. Directive
2004/37/EC on the protection of workers from the risks related to exposure to
carcinogens or mutagens at work[126]
introduces more stringent provisions in the case of carcinogen or mutagen
substances, for example regarding substitution. These
risk management measures include, as also for traditional chemicals, process
control (e.g. various degrees of containment, applying work processes where
nanomaterials are in a fluid matrix instead of in the powder form), local
ventilation and discharge control measures (e.g. filtration), organisational
measures (reducing the number of workers exposed, reducing the exposure time,
etc.) and, as last resort, personal protective equipment. The risks of exposure
due to technical problems (damage, poor tightness) of the containment systems
as well during maintenance and cleaning operations have to be considered. An overview of relevant literature on workplace exposure to
nanoparticles, on risk communication on nanomaterials in the workplace, as well
as company Good Practice examples on the risk management of nanomaterials[127] has been compiled by the European Agency for Safety and Health at
Work (EU-OSHA). An updated list of major information sources with regard to
occupational safety and health (OSH) and nanomaterials, including examples of
risk assessment tools and guidance developed in EU Member States is included in
Appendix 6. By end 2012, EU-OSHA will make a web portal dedicated to OSH and
nanomaterials containing information material for workplaces available on its
website.[128] A tiered pragmatic approach to exposure
measurements and assessment of nanoscale aerosols for workplace operations was
recently developed in Germany in a dialogue between a number of institutions.[129] The approach combines established risk management concepts with
elements of exposure assessment according to the current technology, and it is
based on the experience of the participating practitioners. In order to better understand and improve
the knowledge base on protection of workers from possible risks arising from exposure
to and use of nanomaterials and/or nanotechnology in the workplace, the
Commission has launched a study[130]
aiming to: (i) check the extent to which the current EU OSH legal
framework covers sufficiently and effectively nano-related risks in the
workplace; (ii) delineate a series of possible scenarios that should
help shed light on which options may be better suited to tackling nano-related workplace
risks without undue demands on businesses; and (iii) the drafting of a
practical guidance document that may help tackle the mentioned workplace risks
in waiting for a developed regulatory framework to be put in place. To achieve
this, the study will include an in-depth characterisation of likely exposures of
workers to nanomaterials, relevant risk assessment issues, types and
effectiveness of risk management measures and relevant regulatory issues. The
study is scheduled to be finalised by early 2013. The Commission will also give
consideration to requesting a more robust involvement of the EU-OSHA with a
view to raise awareness and/or disseminate information, as appropriate, in
relation to any possible risks posed by nanomaterials and/or nanotechnology in
EU workplaces. Awaiting the outcome of this study, new
approaches aiming to control workers exposure have recently been presented. An
example is the so-called Nano Reference Values (NRVs) system[131] proposed as provisional alternatives for HBR-OELs[132] or DNELs[133] or US-NIOSH’s approach in recommending an
OEL for TiO2 nanoparticles.[134] This
system is based on a precautionary, thus not on a risk-based approach. While not guaranteeing that exposures below the
NRV-level are safe, NRVs define a maximum generic level for the concentration
of nanoparticles in the workplace atmosphere, corrected for the background
particle concentration. NRVs are intended to be a warning level to urge for
risk management of nanoparticles at the workplace. According to this approach,
when exceeding this level of exposure, reducing measures should be taken. In
any event such measures should also be considered for exposures below the NRVs.
Exposure to consumers and the environment
at the use stage, and to an extent also at the waste stage is more difficult
and often impossible to control through risk management measures at the place
of exposure. There are in principle many tools to manage risks for consumers
and the environment at the place of exposure such as proper
use instructions, disposal or recycling of products.[135]
Nevertheless, as they are not always effective, the
most realistic and promising approach to control exposure to consumers and the
environment, where needed, remains the reduction of emissions at source. In conclusion, where risks are identified,
appropriate risk management measures need to be taken. This includes a range of
possible measures to control exposure at the workplace or minimize exposure to
consumers and the environment through risk management measures at source, and
to the extent possible through measures such as proper use instructions,
disposal or recycling of products. Where the application of current regulatory
obligations such as from REACH registration or the Chemical Agents Directive
may not be sufficiently effective, further regulatory action, including
possible restrictions of use of certain nanomaterials may become necessary. 5. Risk assessment 5.1. The opinions of the EU risk
assessment bodies In light of the benefits derived from
applications of the nanotechnologies and resulting, expected growth of their
presence on the EU market, following an initial mapping of the potential risks
of nanotechnologies in March 2004[136], the
European Commission asked, respectively, the three non-food Scientific
Committees (Scientific Committee on Emerging and Newly
Identified Health Risks (SCENIHR), Scientific Committee on Consumer Safety (SCCS),
Scientific Committee on Health and Environmental Risks (SCHER))[137], the European Food Safety Authority (EFSA)[138], the
European Medicines Agency (EMA)[139], and
the European Chemicals Agency (ECHA)[140] to
address the safety of nanomaterials. SCENIHR concluded that “while risk
assessment methodologies for the evaluation of potential risks of substances
and conventional materials to man and the environment are widely used and are
generally applicable to nanomaterials, specific aspects related to
nanomaterials still require further development. This will remain so until
there is sufficient scientific information available to characterise the
harmful effects of nanomaterials on humans and the environment.”[141] The guidance provided by EFSA (2011)[142] offers a strategy for risk assessment in food and feed. It concerns
(i) characterisation requirements of engineered nanomaterials used in food and
feed and (ii) testing approaches to identify and characterise hazards to human
health during use. The guidance lowers information requirements in the absence
of exposure, i.e., no migration from a food contact material, or of absorption
of engineered nanomaterials as such because of complete degradation/dissolution.
The guidance also flags uncertainties. In the food area, EFSA assessed the safety
of silver hydrosol[143] and titanium nitride[144] for
use as food contact materials. Titanium nitride, silicon dioxide (synthetic
amorphous silica) and carbon black are authorised with specifications as food
contact materials.[145] In the medicinal products area, EMA has
been examining applications of nanotechnologies to medicinal products since
2006.[146] To date, recommendations from the EMA Committee for Medicinal
Products for Human Use (CHMP) has led to the approval of about twenty medicines
based on nanotechnology. They include medicines containing liposomes (microscopic
fatty structures) containing active substances, such as doxorubicin[147]; mifamurtide[148] and doxorubicin[149] and nanoscale particles of active substances, such as paclitaxel[150], aprepitant[151] and sirolimus[152].[153] Marketed medical devices using
nanotechnologies concern a broad range of medical applications, ranging from
traditional medical equipment to sophisticated electronic biomimetic devices
via orthopaedic, dental or cardiovascular implants and novel treatments against
cancer. A report published by the French Health Products Agency (AFSSAPS) on 18
August 2011 lists 17 products in the EU alone.[154] Some
national authorities in the EU Member States have developed specific guidance.
The European Commission envisages addressing the issue of nanomaterials in the
context of the revision of the medical device legislation planned for 2012. In the cosmetics area, the European
Commission mandated the SCCS to develop guidance on nanomaterial risk
assessment, including criteria for their categorisation[155] and assess
four nanomaterials used as UV-filters (titanium dioxide, zinc oxide, ETH-50,
HAA299).[156] On 11 November 2011, SCCS concluded that the use of 10% ETH-50 is
safe for dermal application but that sprays containing
ETH-50 cannot be recommended until additional information is provided. The evaluation
of the other three materials is ongoing. Absence of product recalls The EU has two rapid alert systems, one for
products (Rapid Alert System for Non-Food Dangerous Products, RAPEX[157]) and one for food and feed (Rapid Alert System for Food and Feed,
RASFF[158]). No nanomaterial has so far been recalled under RAPEX or RASFF. 5.2. REACH registration
dossiers In close collaboration with ECHA, the
Commission has assessed how nanomaterials have been addressed in REACH
registration and CLP notification dossiers. At the end of February 2012, 7
registrations and 18 notifications had ticked the voluntary field "nanomaterial"
as the form of the substance[159]. The further assessment identified three groups of registration
dossiers, where a) the registrants recognized nanomaterials (8 dossiers /5
substances); b) substances exist only as nanomaterial (12/9), and c) the assessors
identified nanomaterials on the basis of the particle size distribution (5/5).
It is possible that additional substances with nanoform(s) may have been
registered or notified but were not retrieved from the REACH and CLP database
when the search-term "nano" was not used in any text field in the
dossier or when the other search criteria used were not fulfilled. In the assessed dossiers, different ways
were used to present identification of substances that include or in one case
exclude, nanoforms, and to organize nanoform(s) relevant information. Within
groups a) and b) data could generally be linked to nanomaterial but, in
particular for the a) group, its data quality was often in question due to the
lack of justification or adequate characterisation of the addressed nanoform(s)
or the testing material. For the group c) it was not possible to distinguish
which data are for nanomaterial. These findings can partly be explained by the
absence of detailed guidance to registrants on registration for nanomaterials,
the absence of a definition of nanomaterial and the general wording of the
REACH annexes. 5.3. The conclusions from
RIPoNs on the applicability of the testing strategies to nanomaterials The Commission’s Joint Research Centre
carried out a number of REACH Implementation Projects on Nanomaterials
(RIP-oNs) to evaluate the applicability of the existing REACH guidance to
nanomaterials, and if needed, to develop specific advice on how the guidance
could be updated to better address nanomaterials. Three reports are available: RIP-oN 1 relates to "Substance
identification of nanomaterials". Under REACH, substance identification
determines whether substances must be registered separately or data on the same
substance must be shared between the registrants. The
objective of the project was to evaluate the applicability of existing guidance
and, if needed, to develop specific advice on how to establish the substance
identity of nanomaterials. The opinions of the
participating experts from Member State Competent Authorities, industry, NGOs
and ECHA diverged on several key issues, including whether
size or surface treatment/functionalisation should affect substance identification
or characterization of physicochemical properties. It
was not possible to reconcile these opinions. Therefore, the report[160] mainly describes options/approaches rather than providing explicit
recommendations. ECHA has been asked to develop such recommendations as it starts gaining practical experience through the evaluation of
relevant registration dossiers. The objectives of the RIP-oN 2 report on
"Specific Advice on Fulfilling Information Requirements for Nanomaterials
under REACH”[161] were to provide advice how REACH information requirements on
intrinsic properties of nanomaterials can be fulfilled, including the
appropriateness of the relevant test methods (and dosimetry) for nanomaterials,
and outline, when relevant, possible specific testing strategies. It was also
set to provide advice on the information that is needed for safety evaluation and
risk management of nanomaterials. The objective of the RIP-oN
3 project "Specific Advice on Exposure Assessment
and Hazard/Risk Characterisation for Nanomaterials under REACH" was to develop advice on how to do exposure assessment for nanomaterials
within the REACH context and how to conduct hazard and risk characterisation
for nanomaterials. Neither RIP-oN 2 or
RIP-oN 3 specifically addressed presentation of information on multiple nanoforms
within dossiers (RIP-on 1 task) or the practical implications of multiple
nanoforms of the same substance for chemical safety assessment. The reports
however recognize the possibility, when scientifically justified, to apply the
same data for different forms and substances (read across, grouping) and to use
non-testing approaches (e.g. (Q)SAR, in silico). They also recommend further
research on non-testing approaches as a high priority to be addressed within
the short term. RIPoN 2 concludes that the existing
guidance and the information requirements on (eco)toxicological data (based on
the OECD Test Guidelines and ISO/CEN standards) are considered applicable for
the assessment of nanomaterials. Attention needs to be given to measuring,
dosing, delivery and tracking of nanomaterials in the test system. Representative
sample preparation and thorough and accurate physico-chemical characterisation
using multiple techniques are an essential component of assessing the potential
(eco)toxicity of nanomaterials. The report proposes the introduction of
additional physico-chemical property information requirements and of an
advisory note on sample preparation. The guidance on physico-chemical properties
was considered to be generally applicable to nanomaterials. However, the limited
relevance and applicability of the property and methods for surface tension,
flash point and viscosity was recognized, and the further evaluation of suitability
of existing methods for water solubility, partition coefficient,
adsorption/desorption was recommended. The guidance on toxicological Information
Requirements is considered applicable, although it was highlighted that
attention needs to be given to measuring, dosing, delivery and tracking of
nanomaterials in the test system. In general, the basic ecotoxicological
properties and endpoints described in the OECD Test Guidelines for the
determination of potential effects of test substances in relevant environmental
compartments (aquatic, terrestrial, sediment) after acute or chronic exposure were
considered adequate and relevant for nanomaterials. However, the report
acknowledges the fact that OECD Test Guidelines were not specifically designed
for the testing of nanomaterials, and the guidance provided on important
measurement aspects such as the sample preparation, the delivery of test substances
to test system or the exposure quantifications/metrics, in all of these test
guidelines is considered to be insufficient for testing of nanomaterials. These
issues have been preliminarily addressed in the OECD specific Preliminary Guidance
Notes on Sample Preparation and Dosimetry.[162] The identified potential additional
relevant specific intrinsic properties include: (a)
Physico-chemical properties (Particle shape,
Surface area, Surface energy, Surface chemistry, Surface charge, Redox
potential, Cell-free ROS/RNS production capacity, State of dispersion, State of
agglomeration). Additional guidance chapters were recommended only for shape
and surface area; (b)
Toxicological endpoints (Cell uptake, Cell
viability, Oxidative stress, Inflammation, Fibrosis, Immunotoxicity/sensitisation,
Cardiovascular toxicity); no additional guidance chapter for them was recommended; (c)
Ecotoxicological endpoints, Ventilation rate,
Gill pathologies, Mucus secretion, Brain pathology, Animal behaviour, Oxidative
stress biomarkers[163]; no additional guidance chapter for them was recommended. On certain endpoints[164] there was limited or no body of evidence available to inform the
provision of specific practical advice. The published scientific evidence
demonstrated that representative sample preparation and thorough and accurate
physico-chemical characterisation using multiple techniques is an essential
component of assessing the potential (eco)toxicity of nanomaterials. Factors
such as the exposure method, dose selection, species used, cell type under
investigation, as well as coating/functionalisation of the surface and particle
impurities, release of free metal ions and particle aggregation all have the
potential to impact on the assessed (eco)toxicity of nanoparticles. The full
extent of influence of these factors on (eco)toxicological impact of
nanomaterials is however still emerging. While, in general, it was reported that
only minor updates are necessary to some of the existing Integrated Testing
Strategies (ITS) for the intrinsic properties/endpoints considered, a
substantive update to the ITS for particle size analysis (or granulometry) was recommended,
together with the expressed need to justify scientifically the use of QSAR
and/or read-across. Advice was provided on the scientific basis for the
categorisation of nanomaterials and application of in silico methods,
read-across and category approaches for deriving hazard information for
nanomaterials from the information on bulk substances or from comparison
between nanomaterials. Whilst the lack of data across a wide range of
structural and compositionally different nanomaterials precludes a fully
prescribed category-based approach being developed, the suggested approaches
for possible development indicate where such groupings may be applied. RIPoN 3
concludes that there is still very limited evidence to draw any generalized
conclusions or recommendations for the chemical safety assessment of
nanomaterials under REACH. Known exposure assessment methods are generally
applicable but may still experience methodological challenges, such as how to
distinguish manufactured nanoparticles from background level of natural and
incidental nanoparticles. No new nano-specific risk management measures need to
be developed, but it is important to include specific information on nanomaterials
in the safety data sheets (SDS) and assess the effectiveness of measures in
place to ensure adequate protection. Due to lack of evidence, no recommendation
is provided regarding risk management measures relating to the environment or
the consumer. The exposure
scenarios (ES) case studies performed under RIPoN-3 highlighted general
difficulties with the application of current guidance to nanomaterials. The
‘hierarchy of control’ concept which underpins much of the Operational
Conditions (OC) and Risk Management Measures (RMM) REACH guidance in this area
was considered to be equally valid for nanomaterials as for other substances.
There is evidence that already known control and risk management methodologies can
provide levels of protection for workers from exposure to engineered
nanomaterials. It was not considered necessary to recommend the development of
new nano-specific RMMs. However, the specific protection provided against
specific nanomaterials needs to be evaluated. The project found that current
exposure estimation models are not validated for nanomaterials and should not
be used for nanomaterials without accompanying measurement data or scientific
justification. Emissions to
the workplace may be substantially reduced if a process involving engineered
nanomaterials is performed in a properly designed enclosure/containment,
especially when adequately addressing what happens when the containment is
opened. Worker exposure can be significantly reduced or prevented through the
use of correctly designed and implemented extraction ventilation and
filtration. Filtration theory indicates that filtration will be effective for
particles in the nanometre size range. This also applies to personal protective
equipment, where several studies clearly demonstrate the potential of
respirator filters to capture nanoparticles. As for chemicals in general,
further work is required to evaluate human factors such as leakage around
face-piece filter and test protective suits and gloves. The RIP-oN 3
report states that at current stage, Control Banding (CB) cannot be used to
demonstrate that the risks are adequately controlled, but might support users
in initial selection of control measures. No guidance can be given at this time
as regards preliminary medical surveillance activities, though they are likely
to be beneficial in the long term. Similarly, no recommendations for risk
management measures in REACH guidance relating to the environment or consumer
exposure can be made at this time, due to lack of evidence. For safety data
sheets (SDS), it is important that information provided for a nanomaterial is
representative, valid and provides the protection needed for the forms
addressed by the SDS. Some of the key
issues in exposure estimation are the discrimination from background
nanoparticles and the adequate consideration of high spatial and temporal
variability. The full particle size distribution curve as well as presence of
‘bundles’ or ‘clumps’ of high aspect ratio nanomaterials should be reported
when measuring, and model estimates should not be relied on alone without
scientific justification and further confirmation of their validity in
individual cases. Adequate particle characterisation within test systems as
well as the exposure environment is important as e.g. aggregation/agglomeration
of nanoparticles may affect standard toxicity tests and affect parameters such
as deposition zone in the lung or uptake by organisms. For the most
part, the current guidance in relation to deriving exposure limits provides
sufficient flexibility to address areas of uncertainty, data gaps and, if
justified, deviations from the default approach and the current assessment
factors derived from classical (soluble substance) toxicity. Regarding hazard
and risk characterisation, an alternative approach for extrapolating from
experimental animals to humans for inhalation exposure was suggested for
consideration and development. RIP-oNs 2 and 3
work identified the critical items on exposure/dose descriptors and outlined
needs for adequate exposure assessment metrics/parameters compatible with those
used for hazard assessment. The metrics currently used in risk assessment across
exposure, toxicology and risk, are based on mass or number. Based on
toxicological evidence on inflammation, the most prominent emerging alternative
or additional metric is surface area. With no definitive conclusions on the
best dose metric, there was consensus that there should be sufficient
characterisation of the forms of a substance tested to allow the dose response
to be expressed in the different metrics discussed - number, surface area and
mass. There are other parameters as well which can act as modifiers of the
toxicity, including particle size, size distribution, density, surface modification,
aggregation/agglomeration state and shape, but these parameters would not
generally be considered as scalable dose quantities and do not therefore appear
to conform to the current use of the term “metric” under REACH. A comprehensive synthesis of findings,
implications, issues and advice was developed and integrated through the Task
Reports and the Final Project Report of the RIP-oN2 and RIP-oN3. Where
considered relevant, feasible and justified, specific advice for updating REACH
guidance was provided. For issues which were not currently
technically/scientifically mature for developing detailed guidance, the need
for further research and development was indicated. It must be noted in any
case that the update of REACH guidance and thus inclusion of any of the advice
from the reports into the ECHA guidance is exclusively the responsibility of
ECHA. 5.4. JRC Nanohub The European Commission’s Joint Research
Centre’s (JRC) NANOhub is a comprehensive, non-public IT platform designed for
addressing and hosting information on nanomaterials. It is based on IUCLID,
which provides an accepted basis for regulatory use of data on chemicals in the
EU. With its web-based functionality it is intended to boost interconnections
and to facilitate synergies for collaboration within research projects. It has been developed on behalf of the JRC
as a tool to address nano-safety and measurements of nanomaterials, supported
by an international stakeholder network from academia, industry, Member States,
ISO, CEN, OECD, and NGOs. The JRC NANOhub hosts, among others, data and studies
from the OECD Working Party on Manufactured Nanomaterials (WPMN) sponsorship
programme on the safety testing of a representative set of nanomaterials, as
well as test and measurement results on materials from the JRC Repository of
Representative Nanomaterials (see also Appendix 9). The data structure builds on IUCLID
chapters and on the OECD Harmonised Templates. These chapters have been
expanded to add additional templates for nanomaterial-specific endpoints listed
by the OECD WPMN in the Guidance Manual of the sponsorship programme.[165] Once these new templates have been tested and finalised, they will
be submitted to the OECD for harmonisation and possible implementation in
IUCLID. JRC NANOhub provides features to address
data quality, to create reports and dossiers, and to exchange data, and it
provides collaborating parties with a facilitated frame for hosting and sharing
data. In this way it facilitates cooperation between international parties and
research projects using the World Wide Web. JRC NANOhub consists of
independent, consortium-specific installations hosted by the JRC with options
to protect confidentiality but also to share results between different
consortia. A listing of hosted projects can be found on www.nanohub.eu. 5.5. Organisation for Economic
Co-operation and Development: Working Party on Manufactured Nanomaterials In 2006 the OECD Working Party on
Manufactured Nanomaterials (WPMN) was established, bringing together relevant
Ministries and Agencies responsible for human and environmental safety, as well
as representatives from other stakeholder groups. A formal four-year programme of work was
endorsed by the OECD Chemicals Committee to cover the period 2009 to 2012 which
aimed at the development of a globally harmonised approach to the management of
nanomaterials. The WPMN published a booklet[166] in February 2011 summarising the first five years of the programme,
noting in that report its work on: ·
Testing specific nanomaterials for their human
health and safety evaluation, while ensuring appropriate testing methods (in
vivo & in vitro), in addition to promoting the development of
alternative test methods to nano-toxicity testing; ·
Promoting co-operation on voluntary schemes and
regulatory programmes; ·
Facilitating international co-operation on risk
assessment strategies; ·
Developing guidance on exposure measurement and
exposure mitigation at the workplace, for consumers and for the environment;
and; ·
Promoting the environmentally sustainable use of
nanotechnology through enhancing the knowledge base about life cycle aspects of
manufactured nanomaterials. This should be done at their different stages of
development and applications. This work has
already started to generate guidance literature for those working in this field
such as 'Preliminary Guidance Notes on Sample Preparation and Dosimetry'[167] and a 'Guidance Manual for the Testing of Manufactured
Nanomaterials (First Revision)'.[168] A
full list of relevant OECD publications can be found on the dedicated WPMN
website.[169] The ninth
meeting of the WPMN took place in December 2011 to examine progress made on the
current work plan. The tenth meeting of the WPMN is scheduled for June 2012. 5.6. Strategic Approach to
International Chemicals Management (SAICM) In 2006 the International Conference on
Chemicals Management (ICCM) adopted the Strategic Approach to International
Chemicals Management (SAICM).[170] This
provides a UNEP level policy framework to promote chemical safety around the
world. In May 2009 ICCM2 adopted Resolution II/4
on emerging policy issues which covered the specific issue of nanotechnologies
and manufactured nanomaterials, recognising their potential benefits and
potential risks to human health and the environment. Since then work has been taken forward to
build a fuller understanding of this issue. The above Resolution prompted a
number of Regional workshops on the issue led by UNITAR and the OECD and also
the drafting of a Report[171] on nanomaterials within the context of SAICM which was presented to
the SAICM Open Ended Working Group in November 2011. Also during this meeting
work was undertaken to develop actions that could be added to the Global Plan
of Action (which acts as a guidance document and working tool to support implementation)
in due course. This issue will be revisited during ICCM3 which is due to take
place in September 2012. 5.7. Research on nanomaterial
safety The European Commission has started funding
projects specifically addressing nanosafety since the 5th EU
Framework Programme for Research and Technological Development (FP5, 1998-2002),
with a regular budget increase. So far, 46 nanosafety projects have been funded.
They represented a total EU investment of 130 M€ (corresponding to a total
projects costs of 185 M€). The framework programme calls are conceived to cover
all aspects necessary for the risk assessment and risk management of
nanomaterials: physico-chemical characterisations of nanomaterials, fate and
behaviour in biological and environmental media, bio-nano interactions,
nano-toxicity and nano-ecotoxicity, life cycle analysis of
nanomaterial-embedded products (including recycling and final treatment),
measurement devices, exposure, worker protection, risk assessment tools and
risk management strategies. The EU projects are requested to join
forces through the NanoSafety Cluster to maximise synergies, to facilitate the
formation of a consensus on nanotoxicology in Europe; to improve the coherence
of nanotoxicology studies and harmonize methods; and to provide a single voice
for discussions with external bodies and to provide industrial stakeholders and
the general public with appropriate knowledge on the risks of nanoparticles and
nanomaterials for human health and the environment. 6. Information and databases on the use of
nanotechnology and nanomaterials The European Parliament has called on the
Commission to compile “an inventory of the different types
and uses of nanomaterials on the European market, while respecting justified commercial
secrets such as recipes, and to make this inventory publicly available”. [172] The Council invited the Commission to “evaluate the need for […]
the further development of a harmonized database for nanomaterials, while
considering potential impacts.” [173] While the European Parliament does not
specify the meaning of the term “inventory”, in particular on whether this
inventory should be presented in the form of a document or database, the
Council invites the Commission to evaluate the need for the further development
of a harmonized database. The Commission therefore has, in addition to the
information on types and uses of nanomaterials in section 3 and Appendix 2 of
this document, compiled information on existing databases in section 6.1 and Appendix
8. Section 6.2 gives information on plans to set up a European Commission web
platform on nanomaterial types and uses, including safety aspects. 6.1. Existing databases on, or
with relevance to, nanomaterials on the market Databases on nanomaterials on the market
can in principle be structured either from the perspective of nanomaterials (and possibly cover their uses
in products in more or less concrete terms) or from the perspective of products
on the market containing nanomaterials. Both approaches have been used in different
existing databases. There are also databases which have elements of both. In
addition, the nature of databases differs largely. An overview of existing
databases is contained in Appendix 8.[174] A database with a clear substance-structure
is REACH-IT.[175] REACH registrations for substances are stored in the REACH-IT
database. REACH is specific for substances and it is possible to indicate that
the registered substance is a nanomaterial or includes nanoforms in REACH
registrations (for example, there is a voluntary tick-box to identify the
substance or form of a substance as a nanomaterial). There is also ECHA advice
on how to enter relevant data in IUCLID. This information is retrievable from
the registration database. It is however not always easy to identify which
information relates to the nanoform(s) and which information to the bulk
form(s) of the substances. Also, the description of uses in REACH dossiers is
rather generic, and therefore it is not possible to identify concrete
applications from the REACH dossiers. A screening of the REACH registration
dossiers and CLP notifications was performed to identify information about
substances in the nanoform. Methodology and outcome of this work is reported in
Appendix 3. An example of a mixed database is ObservatoryNano.[176] Although the main aim of the database is not an exhaustive
inventory of nanomaterials and their uses on the market, it contains a number
of factsheets, briefings and reports which give an overview of nanomaterials,
as well as product areas in which those substances are used. The database has a
relatively strong focus on new developments in terms of research and
innovation, and therefore does not always distinguish between widespread
commercial use of nanomaterials and applications at the pre-market stage. Moreover, there is a series of databases
focusing on products on the market containing nanomaterials. Examples for such
databases include the Woodrow Wilson database (“The
Project on Emerging Nanotechnologies”)[177], the ANEC-BEUC 2010 inventory of consumer products containing
nanomaterials (ANEC-BEUC 2010)[178], the
online database of the German Environmental NGO ‘BUND’ (Friends of the Earth
Germany)[179], and the nanotechnology products database of Nanowerk.[180] Those databases are all attempts to collect as much information as
possible on products containing nanomaterials at the level of individual
products and brands. However, they are neither based on systematic data
collection over a wide range of products, nor is it certain that the products
mentioned indeed contain nanomaterials. This is because the databases are at
least partly based on claims by manufacturers which may, or may not be correct.
Given the multitude of applications identified in the course of the analysis of
nanomaterials on the market (see Appendix 2) and the limited number of products
identified (e.g. around 1300 products worldwide for the Woodrow Wilson
database), it seems however likely that those databases only cover a very small
fragment of products containing nanomaterials on the market. There are also a number of voluntary one-off
reporting schemes in EU Member States such as the United Kingdom, France,
Denmark, Germany and Ireland, as well as in several non-EU countries.[181] However, those schemes only received very little feedback and generally
do not give a satisfactory overview of nanomaterials on the market. France has
recently introduced regulatory measures for a mandatory registry for substances
at nanoscale, mixtures from which nanomaterials can be released, and articles
with an intended release of nanomaterials. In addition to the product databases listed
above, an overview is presented in Appendix 8 on databases not predominantly
considering products, but containing information related to the potential
toxicity or hazard of nanomaterials. Two of those databases provide information
on experimental data and the projects and/or organisations in which these data
are obtained. Two other databases specifically focus on industry needs. (2)
The OECD Database on Research into Safety of Manufactured Nanomaterials (3)
JRC NanoHub (4)
nanotech-data.com (5)
nanoproducts.de 6.2. Plans for a European
Commission web platform on types and uses of nanomaterials, including safety
aspects The interest in an inventory/harmonised
database expressed by the European Parliament and the Council reflects a widely
perceived lack of information on nanomaterials on the market. Existing
databases are either not clear enough on the types of uses of nanomaterials, or
are rather sketchy and incomplete in terms of products containing
nanomaterials. In some cases, there is little quality control of the
information, and therefore there are doubts on the factual correctness of at
least part of the contained information. The Commission therefore has gathered
available information in Appendix 2 to this Staff Working Paper. However, the Commission understands that
there is an interest in keeping this information updated and completed by new
information on nanomaterials and products containing nanomaterials. The
Commission is ready to host an inventory in the form of a web platform on
nanomaterials and their uses. Preparatory work to set up such a web platform,
led by the Commission’s Joint Research Centre, has already started. Discussions
among the responsible Commission services on capturing specific requirements
have been initiated in order to support the European Commission's policies such
as environment, consumers, health, business, employment and innovation. The web platform should enable the user to
retrieve comprehensive information on nanomaterials, presenting that information
in an easily searchable way and linking to the main information sources and
databases. This web platform will both present general summary information on
nanomaterials and their uses, including safety aspects, building on the present
Staff Working Paper, and link up to and build upon various existing or planned activities
(e.g., JRC NANOhub, OECD WPMN, French Grenelle 2 bill, and others). Depending
on the intended users of such a web platform (consumers, downstream/workplace
users, regulators, researchers) it is necessary to consider what kind of
information should be available to these different groups, and certain
filtering mechanisms should be considered. A web platform design would be
advantageous which would be able to incorporate existing information and be at
the same time capable of being adaptable to future options. Strengths and weaknesses of existing
databases on nanomaterials and/or products containing nanomaterials are being
analyzed. Publicly available databases/inventories of nanomaterials and their
use often lack clear criteria for inclusion, quality assurance of the data
content and being up to date. These shortcomings should be addressed, and for
the part of information handled under the responsibility of the Commission,
appropriate quality assurance, sustaining and periodic updating of the
information should be guaranteed. Work towards a harmonized European web
platform will benefit from the recently concluded project on “Development of an
inventory for consumer products containing nanomaterials” carried out by RIVM
on behalf of the Commission.[182] A data model was already developed in that project to record a
multitude of nanomaterial relevant information related to a product in a
structured manner. Furthermore, a methodology was developed to identify
consumer products on the EU market containing nanomaterials, and it was
subsequently used to populate a pilot version of a searchable database
containing such products. When setting up such a harmonised
Commission database it will also be necessary to take into account the
situation in Member States where regulatory measures (France) or discussions
were already initiated in parallel to activities within the Commission. Appendix 1
Types of nanomaterials 1. Introduction This Staff Working Paper is focused on the
materials that meet the EU definition of nanomaterial (see Chapter 2).
The EU has defined this single term while being well aware of the heterogeneous
range of materials it covers, as shown in Chapter 3. This appendix provides an
overview of the most important and common types or subcategories of
nanomaterials, based on the EU definition of nanomaterial, but using also the
more extensive nanomaterial terminology developed by ISO.[183] The appendix thereby also intends to clarify the relation between
the EU and ISO nanomaterial definitions. Section 1 explains and defines a number of
basic terms which are used to describe and categorize nanomaterials. Section 2
lists the types of nanomaterials which are covered by the current EU definition
of the term "nanomaterial". Section 3 discusses materials which do
not comply with the current EU definition, but which fall under the scope of the
broader ISO definition of nanomaterial, and which may have to be considered
in the review of the current EU definition, scheduled before end 2014. 1.1. Basic terms and
definitions Nanoscale The key term in most of the definitions of
terms used in nanotechnology and nanosciences is the term nanoscale.
Unless otherwise specified, and in accordance with ISO and EU practice, this
term has in this document been used as short for the range from 1 nm to 100 nm.[184] Nano-objects ISO/TC 229 (the ISO Technical Committee on
Nanotechnologies) invented the word nano-object and defined it (first in
ISO/TS 27687:2008, later confirmed in ISO/TS 80004-1:2010) to describe
particles which have at least one of their 3 (orthogonal) external dimensions
in the nanoscale.[185] Several subclasses of nano-objects are distinguished, such as nanoparticles
(nano-objects with all 3 external dimensions in the nanoscale), nanofibres
(grouping nanorods and nanotubes), and nanoplates.[186] All particulate materials consisting for more than 50 % of
nano-objects fall under the EU definition of nanomaterial. Aggregates and agglomerates, primary and
secondary particles Nano-objects, like other particles, have a
natural tendency to agglomerate: they form groups which are held together by
weak forces (e.g., van der Waals forces) or by simple physical entanglement.
The tendency to form agglomerates generally increases with decreasing
particle size due to the higher surface energy and because inertial forces,
which can 'deconstruct' agglomerates for example during sonication, become
relatively less important with decreasing volume/surface area ratio. Often, nano-objects are encountered in the
form of aggregates. Aggregates are groups of particles which, unlike
agglomerates, are held together by strong forces (for example covalent chemical
bonds) or by complex physical entanglement. Aggregates are most often created
during the processing of the nano-objects, e.g., when they are formed in a hot
gaseous phase and collide with each other at a temperature above or near to
their melting temperature. Both aggregates and agglomerates are also
called secondary particles, as they consist of groups of smaller,
so-called primary particles. It is difficult and often impossible to
turn aggregates back into individual primary particles other than by
high-energy processes such as mechanical milling or abrasion. On the other
hand, the number of primary particles in an agglomerate can change easily,
e.g., under the influence of changing environmental conditions.
Correspondingly, the methods to distinguish between agglomerates and aggregates
are based on the detection of the change in size of the secondary particles
upon sonication or upon the change of pH or other environmental conditions. Both agglomerates and aggregates of
nano-objects are covered by the EU definition of nanomaterial. Nanostructure The current ISO definition for
nanostructure is 'a composition of inter-related constituent parts, in which
one or more of those parts is a nanoscale region, where a region is defined by
a boundary representing a discontinuity in properties'[187]
Examples of a nanoscale region are nanophases or nanopores. Dispersion A dispersion is a material that consists of
a dispersing medium (a continuous, matrix phase) and a dispersed phase (a
collection of particles or small phases of the same kind, which are separated from
each other by the dispersing medium). Both the dispersing medium and the
dispersed phase can be solid, liquid or gaseous, leading to a number of
possible combinations: || Dispersed phase Continuous phase || solid || liquid || gas solid || (kind of) composite material || porous material filled with liquid || porous material filled with gas liquid || suspension || emulsion || foam gas || aerosol || aerosol || (does not apply) 1.2. Nanomaterials – general
definitions The EU definition of nanomaterial The EU definition of nanomaterial has been
shown in Chapter 2 of this Staff Working Paper, which explains how the
definition was developed and on which materials it is focused. In the Recommendation on the nanomaterial definition, the Commission
commits to review its current definition by December
2014, in the light of experience and of scientific and technological
developments. In particular, the review should assess whether the number size
distribution threshold of 50 % should be increased or decreased and whether to
include materials with internal structure or surface structure in the nanoscale
such as nanoporous and nano-composite materials. For this reason, it is useful
to look also at the current ISO definition, which is broader and inter alia
includes nanostructured materials other than aggregates and agglomerates. The International Organization for
Standardization (ISO) definition of nanomaterial Section 1.1 lists a number of terms and
concepts used to describe features of materials that are called nanomaterials.
ISO has used these terms in its definition of the term nanomaterial in its
Technical Specification 80004-1[188]: “A nanomaterial is a material with any
external dimension in the nanoscale or having internal structure or surface
structure in the nanoscale Note 1: This generic term is inclusive of
nano-object and nanostructured material. Note 2: See also engineered nanomaterial,
manufactured nanomaterial and incidental nanomaterial." As is the case for all ISO Technical
Specifications, this definition will have to be confirmed in a full ISO
standard, or be revised.[189] Some of the questions to be solved are: –
is one single nano-object a nanomaterial?
–
since all materials have a structure at the
nanoscale, is everything a nanomaterial? The first question is implicitly answered
in the EU definition, which considers nanomaterials to be particulate materials
with a particle size distribution. Single nano-objects do not have a particle
size distribution, and have no industrial or market relevance. It is expected
that ISO will consider, inspired also by the EU definition, an additional term
such as particulate nanomaterial to cover 'materials consisting of
nano-objects'. The second question is one of the reasons
why nanostructured materials are not covered by the current EU definition. ISO
has considered the issue of nanostructured materials in the recently released
ISO TS 80004-4 (Nanotechnologies – Vocabulary – Part 4: Nanostructured
Materials)[190], which limits the nanoscale features that can turn a material into
a nanomaterial, in the following way: "A material should not be classified
as nanostructured based solely on its crystalline properties (three-dimensional
arrangements of atoms or molecules forming a crystallite, short range order of
atoms in amorphous or quasi-amorphous phases, grain boundaries, intragranular
interfaces, dislocations, etc.). In contrast, materials with a grain size
distribution having a significant fraction of grains in the nanoscale
(nanocrystalline), voids and pores in the nanoscale, or precipitations in the
nanoscale (i.e., nano-objects in a solid matrix) are sufficient features for
materials to be classified as “nanostructured” (see ISO/TS 80004-1, 2.4
nanomaterial). Similarly, almost all materials always have surfaces with
morphological and chemical heterogeneities in the nanoscale. Only surfaces that
have been intentionally modified or textured to have morphological or chemical
heterogeneities in the nanoscale identify materials as “nanostructured”." 2. Types of nanomaterials matching the EU
definition A number of materials meet both the current
EU and ISO nanomaterial definitions. Basically, these are the particulate
nanomaterials, which consist of nano-objects or contain a major fraction
thereof. 2.1. Nanostructured powders and
nanopowders A powder is an assembly of discrete
particles usually less than 1 mm in size.[191] According
to ISO/TS 80004-4 a nanostructured powder is a powder comprising nanostructured
agglomerates, or nanostructured aggregates, or other particles of
nanostructured material. In this definition, the nanostructured aggregates and
agglomerates are collections of individual nano-objects, and therefore they
match the EU definition. It must be noted that no term has yet been
assigned to powders consisting of non-aggregated and non-agglomerated nano-objects.
ISO has the intention to close this gap, possibly using the term nanopowder. Conceptually
even simpler than nanostructured powders, nanopowders seem to be the most
straightforward kind of nanomaterials, matching also the EU definition. However,
the term is of limited practical relevance given the strong tendency of
nano-objects to agglomerate. To avoid the agglomeration of nano-objects, they
need to be dispersed in liquid (see section 2.2). The family of nanostructured powders and nanopowders
can be subdivided based on the shape of the included nano-objects (equiaxial:
nanoparticles; elongated: nanofibres, nanotubes or nanorods; flat: nanoplates).
Alternatively, subdivisions can be made based on the element or compound of
which the nano-objects consist. It is possible, at least in theory, to produce
nanostructured powders of almost all elements or compounds which at ambient
conditions are in the solid state (metals, polymers, ceramics). 2.2. Nanosuspensions A nanosuspension consists of solid
nano-objects suspended or dispersed in a liquid phase. A common term to denote
a similar class of materials is the term 'colloid'. (Note: The upper size limit
of the particles in a colloid system varies in different definitions of the
term between 100 nm[192] and 1000 nm.[193]) 2.3. Nano-aerosols Nano-aerosols are materials which consist
of a gaseous phase containing freely moving nano-objects. It is not
straightforward to produce nano-aerosols with sufficient stability to allow
trade and transport. Rather, these materials are produced, intentionally or
unintentionally, at a certain place and time. Both intentionally and
unintentionally produced nano-aerosols are relevant from a regulatory
point-of-view, and are included in the EU definition of nanomaterial, if the
dispersed particles are solid. 3. Types of nanomaterials not matching the EU
definition A number of materials meet the ISO (or other)
nanomaterial definition(s), but not the EU definition. Basically, these are
nanostructured materials and materials containing liquid or gaseous 'particles'.
The more common kinds of these materials are listed below. 3.1. Nano-emulsions Nano-emulsions consist of liquid
nano-objects suspended or dispersed in a liquid phase. They are not covered by the
EU nanomaterial definition, because the term particle as defined in the
Commission Recommendation is intended to cover only nano-objects with a defined,
rigid shape[194], thus in essence solid nano-objects. 3.2. Particles with an
engineered nanoscale internal structure (if larger than 100nm) Nano-objects are particles with at least
one external dimension at the nanoscale. There are an increasing number of
particles which are engineered to have internal nanoscale features. Examples
are core-shell particles and nano-encapsulates. These particles
may be designed, for example for pharmaceutical applications, where the inner
core particle is "released" in a certain environment. Some of these
materials have an external diameter smaller than 100 nm, matching the EU
nanomaterial definition, others have an external diameter larger than
100 nm, not matching the EU nanomaterial definition. In ISO terms also the
latter qualify as nanomaterials, based on the nanoscale thickness of their
shell or capsule or based on the nanoscale diameter of the core particle. 3.3. Nanocomposite materials Nanocomposite materials (or nanocomposites)
consist of at least two different phases, at least one of which has nanoscale
features. Well-known examples are matrix materials reinforced with carbon
nanotubes (e.g., polymer matrix composites with finely dispersed nanotubes for
improved electrical conductivity). There is a debate about the need to include
more 'traditional' materials under this definition, such as steels or other
metals, which often have a carefully designed microstructure with nanoscale
elements such as precipitates, which improve for example the mechanical
properties of the material. 3.4. Nanoporous materials and
nanofoams Nanoporous materials Nanoporous materials are materials
containing a fraction of small, nanoscale pores. The defining property here is
the size of the nanopore. As such, they are not covered by the nanomaterial
definition (e.g. zeolites). However, when the nanoporous materials consist of
aggregates/agglomerates of particles in nano-size (see Chapter 2.1), they fall
under the EU definition (e.g. silica gels). Liquid nanofoams A liquid nanofoam consists of nanoscale gas
bubbles surrounded by liquid struts. They are not covered by the EU
nanomaterial definition, because the term particle as defined in the Commission
Recommendation is intended to cover only nano-objects with a defined, rigid
shape[195], thus excluding gas bubbles. Solid nanofoam and nanoporous material A solid nanofoam consists of nanoscale gas
bubbles surrounded by solid struts. The defining property can be either the
size of the nanopores or the scale of the strut material. Also, the material
can contain two continuous phases, if the pore volumes are interconnected, in
which case it is the cross-section or thickness of the solid struts that has to
be in the nanoscale. A nanoporous material is a solid material
containing nanopores. The term is overlapping with the term nanofoam, but the
fraction of pores in the nanoporous materials is more limited than in a
nanofoam. 4. Summary Table The table below schematically presents the
types of nanomaterials mentioned in sections 2 and 3. The types in italics
match the EU definition of nanomaterial, with the additional condition that the
number of nanoscale particles in the material exceeds 50 % in the particle
number based particle size distribution. || MATERIALS CONSISTING OF NANO-OBJECTS || NANOSTRUCTURED MATERIALS || || Powders of: - nanoparticles - nanoplates - nanofibres || Powders of nanostructured particles: - aggregates/agglomerates of nano-objects - particles with an engineered nanoscale internal structure (e.g. core-shell particles and nano-encapsulates with external diameter > 100 nm) || Fluid dispersions of nano-objects: - nanosuspensions - nano-emulsions - aerosols of solid nano-objects - aerosols of liquid nano-objects || Fluid dispersions of nanostructured particles: - aggregates/agglomerates of nano-objects - particles with an engineered nanoscale internal structure (e.g. core-shell particles and nano-encapsulates with external diameter > 100 nm) || || || Nanocomposite materials || || Nanoporous materials || Nanofoams - liquid nanofoams - solid nanofoams Appendix 2
Nanomaterials on the EU market 1. Introductory remarks and information
sources This appendix is intended to give an
overview of the nanomaterials on the market as well as their uses. Its focus is
on giving an overall picture of the market, rather than being exhaustive or
concrete in specific applications. Most of the information is taken from SRI
Consulting reports.[196]
Those reports are explicitly referenced to where they concern numbers or
estimates but not where they concern general information. The general
information on nanomaterials on the market and their applications is normally also
from those reports if not otherwise quoted. In addition and on specific
subjects not covered by those reports, the chemistry and materials sectoral
reports of ObservatoryNano[197],
the DaNa Knowledge Base Nanomaterials[198]
or other public sources were used. Where available, information is included on
coverage of nanomaterials in REACH dossiers and classification and labelling by
registrants. This information was taken from the ECHA website[199] and the ECHA analysis on “Information
on Nanomaterials retrieved in the ECHA Databases for REACH Registrations and
CLP Notifications” (see Appendix 3) as well as joint work between ECHA and the
Commission services analysing a number of registration dossiers in more detail.
The classification information is mostly (though not always) unspecific and it
is difficult to deduce whether the information provided relates to the bulk or
nanoform(s) of the substance. Information on the reasons for
(non)classification (e.g. data lacking, conclusive but not sufficient for
classification, etc.) is given in footnotes. Moreover, this appendix takes into
account contributions received as a result of a consultation of the members of
the REACH and CLP Competent Authorities Subgroup on Nanomaterials (CASG(Nano),
including representatives from Member States, industry and non-governmental
organisations)[200]
on a draft of this appendix. Safety information is taken mainly from the ENRHES
report[201],
EU-OSHA and the DaNa Knowledge Base Nanomaterials.[202] In principle, this appendix follows the
definition of nanomaterial as laid down in Commission Recommendation 2011/696/EU. However, in most cases the same
substance exists in particle sizes below and above 100 nm, and it is sometimes
unclear whether the collected information refers to one or the other, or both.
Normally, this is indicated in the relevant sections. This appendix is in
principle structured according to chemical substances
which are nanomaterials or have forms which are nanomaterials.[203] This follows in essence the REACH substance definition, without
prejudice to whether the substance only exists as nanoform or whether the
substance has different bulk and nanoforms. The presented information may
either refer to the substance as such or to specific nanoforms, or, in certain
cases to groups of substances (e.g. polymers) or even broader material
categories (e.g. quantum dots). This is done because it would not be possible
to strictly distinguish all relevant information according to substance or
form. Therefore, this listing is a pragmatic way to present information in the
most structured way possible but not a scientific categorisation. While aiming
at a structured approach in describing the different nanomaterials addressing
the relevant features, the level and detail of presented information varies
significantly. This is because of strong differences in the quality and detail
of information that could be found. If information that is given for some
nanomaterials is missing for others, this normally means that relevant
information could not be identified or was of a quality which was considered
insufficient for presentation in this context. In the context of REACH
registrations, the absence of information normally means that no relevant
registration could be identified. Where appropriate, clarification as to
whether information relates to bulk or nanoforms is provided but often this is
not possible and the information is presented as relating to the “substance”
(in particular in the context of REACH registrations). There are also
variations of the substances, reaction masses[204] etc. which have been
registered in addition to the below list but which are not detailed here
because there is insufficient information to link them clearly to available
market information. In general, the below information is
focused on applications already on the market (including medical applications).
Applications at the stage of research and development (R&D) are normally
not specifically mentioned, although it cannot be excluded that some of the
information relates to products at R&D stage. There are also new types of
nanomaterials in development, which are often referred to as “second
generation” (targeted
drug delivery systems, adaptive structures and actuators), “third generation”
(novel robotic devices, three-dimensional networks and guided assemblies), and
“fourth generation” (molecule-by-molecule design and self-assembly
capabilities) nanomaterials.[205],[206],[207] However, those are either at research or
development stage or at an early stage of market development. Due to the
limited available information on those materials, they are not further
considered in this Staff Working Paper. Military applications are normally not
mentioned. In most applications, the nanomaterial is present in the final
product, either as aggregates or agglomerates (rarely, if at all, as free
particles) in a mobile form or bound in a matrix or included in closed
applications. There may, however, also be cases where the nanomaterial is only
used as an ingredient for the production of the mentioned applications, during
which the nano-ingredient loses its particulate character (through dissolution)
or its nanoscale character (through particle growth or fusion). This appendix aims to give a good and
structured overview of nanomaterials on the market. It can, however, not give a
complete or exhaustive list of nanomaterial forms or variations which are often
tailored in a very specific way to achieve desired properties, and which may
also to a certain degree have different toxicological and ecotoxicological
properties. Depending on the concrete cases, these differences may be smaller
or larger. Therefore, wherever in this appendix reference is made to the
nanoform, this is often not one singular form but refers to variations in
particle size, shape, surface treatment, functionalisation etc. In preparing this appendix, the European
Commission also aimed at identifying information on the relevant competitive
position of EU companies and production sites, as well as on market volumes for
the EU. However, in general it appears that most substances are produced all
through the industrialised world, with producers in Europe, North America
(mainly United States and Canada) and Japan or other traditionally
industrialised countries in the Far East. Often there are also producers in
newly industrialised countries such as China, India, Russia or Brazil. However,
data on producers are not complete, both for the industrialised countries and
even more so for emerging countries. Therefore, it does not seem possible to
give a robust picture of EU companies and production sites per substance. Rather,
the broad impression is that most of the mentioned substances are produced in the
EU at a comparable[208]
level to other industrialized regions, and only for few of those substances
there seems to be a concentration in a particular world region. For this reason,
and due to a lack of specific data for the European Union or Europe as a whole,
reference is made mainly to global data. Equally, most applications of nanomaterials
seem to be marketed throughout the industrialized world. Therefore, it is
difficult to assess whether a particular application is available on the EU
market as opposed to other geographic regions. However, for most of the
applications mentioned below, there is no reason to assume that they are not
present in the EU market. All quoted production volumes are annual
production volumes, unless specified otherwise. Monetary figures are mostly
converted from US$ to € at an exchange rate of 0.785, with appropriate
rounding. 2. Inorganic Non-Metallic Nanomaterials 2.1. Synthetic amorphous silica
(silicon dioxide, SiO2, EC Number 231-545-4) There are various forms of synthetic
amorphous silica placed on the market, including precipitated silica, silica
gels, colloidal silica or silica sols and fumed or pyrogenic silica. Most forms
are either used as stable dispersions of non-agglomerated SiO2
particles (colloidal silica) or as agglomerated or aggregated particles (other
forms of silica). Synthetic amorphous silica has been in use
since the 1920ies. According to SRI, the global consumption of all types of
synthetic amorphous silica was around 1.5 million tons in 2010, with a market
value of around 2.7 bn€. Colloidal silicas are stabilised dispersions
of non-agglomerated, mostly spherical SiO2 particles. The main uses
are in paper industry (e.g. providing anti-slip properties; retention aids and
in coatings of ink jet paper; better handling of recycled paper);
chemical-mechanical planarisation (CMP) slurries (e.g. polishing agent for Si
wafers used to produce computer chips); coatings, paints, inks and adhesives
(increasing strength, scratch and abrasion resistance); precision metal casting
and refractory (e.g. moulds for casting around wax originals); food industry
(e.g. as an aid for clarifying wine, beer, fruit juices etc.); bulk plastics
and composites; photography; metal surface treatment; catalysis; textile;
leather; and building industry (e.g. thermal and acoustic insulation). Precipitated silica is made up of primary
particles in the size range of around 5-100 nm[209] which are aggregated and
agglomerated in the final product. The biggest use of precipitated silica is for
the reinforcement of elastomer products, primarily automotive tyres, footwear,
rubber articles and cable sheathing. In tyres, formulations using precipitated
silica reduce rolling resistance, improve traction under slippery conditions
and improve fuel efficiency. Precipitated silica is also used in batteries; as
antiblocking agent in thermoplastic films; as carrier silica for liquids and
semi-liquids and anti-caking agent in food powders, in health care products
such as toothpastes, detergents and cosmetics; as matting agents in paints and
varnishes; in the paper industry as advanced fillers in newsprint paper and in
special coated papers for inkjet and direct thermal printing to enhance ink
absorption; and in agricultural products. Synthetic silica gels are products of the
polymerisation process of fine colloidal silica. They have a similar structure
as precipitated silica, the difference being that the cross-linked silica
particle networks form a nanopore structure that is finer than the pore
structure of the aggregated particles in precipitated silica. Silica gels are
sold in various types of gels (hydrogel, aerogel, xerogel, etc.). They are used
in many food and health products (e.g. to selectively remove certain proteins
and polyphenols that precipitate upon chilling). They are used in food industry
as an anticaking agent and as a carrier for vitamins and as a tableting aid in
pharmaceuticals. They are also used in cosmetics such as face powders, as flow
conditioner and for oil absorption. Silica gels also serve as drying agents,
protecting a wide variety of products during shipment and storage. They are
also used in paints, catalysts, paper coatings etc. Pyrogenic (fumed) silica is manufactured by
using the high temperature hydrolysis process developed in the beginning of the
1940s. It consists of agglomerated and aggregated primary particles. The latter
are of size typically between 5 and 100 nm. The aggregates, which are fused and
chemically bonded primary particles, typically are of size between 100 nm and
350 nm. The aggregates in turn form agglomerates typically in the range from
150 nm up to the several 100 µm.[210]
Pyrogenic or fumed silica[211]
is used in silicone rubber applications, as a reinforcement and thixotropic
agent in plastics, gel coats, sealants and adhesives, cosmetics and
toothpastes; in coatings and printing inks; as a free flow, antistatic agent in
animal feedstuffs and hygroscopic powders; and carrier for active ingredients.
It is also used as an antifoaming agent in the manufacture of paper,
decaffeinated coffee and tea, poultry and seafood processing, and oil refining.
The substance silicon dioxide (synthetic
amorphous silica) has been registered under REACH.[212] Given the explanations in the
registration dossier, referring to amorphous silica, fumed and precipitated
silica, it seems however clear that the dossier mostly, if not exclusively
relates to the nanoform. It has not been classified as hazardous by the
registrant.[213] Animal data show that synthetic amorphous
silica, at very high doses, can induce (mostly reversible) inflammation,
cytotoxicity and tissue damage in the lungs.[214]
However, treatment with lower doses is observed not to effect toxicity in
animals.[215]
ECETOC has made a critical evaluation of the physico-chemical properties,
toxicology, ecotoxicology and environmental fate and impact of
(non-crystalline) synthetic amorphous silica.[216] In its opinion of 5 June 2009, the EFSA
Panel on Food Additives and Nutrient Sources concluded that the use of silicon
dioxide up to 1500 mg SiO2/day and of silicic acid gel to supply up to 200 mg silicon/day,
added to food supplements, is of no safety concern.[217] Synthetic amorphous silica (primary
particles in the size range 1-100 nm) needs to be distinguished from respirable
crystalline silica (primary particles mostly above 100 nm). Contrary to
synthetic amorphous silica, crystalline silica is known to produce silicosis, a
serious chronic lung disease observed in particular with workers who have
inhaled particles of crystalline silica.[218]
Workplace exposure can occur at production,
use, when machining materials and from waste and depends on the work procedure
and applied risk management measures. Exposure to humans and the environment at
the use/consumption and waste stages varies according to application. Exposure to humans can be significant when the amorphous silica is
ingested from food, or in cosmetics and pharmaceutical applications. An important source of environmental exposure is wear of tyres.[219] 2.2. Substances similar to
synthetic amorphous silica There are several substances which are
similar in characteristics and applications to synthetic amorphous silica.
Although they have not been widely discussed under the aspect of nanomaterials,
and hence information is scarce about applications of possible nanoforms of
these substances, they are likely to be at least partly nanomaterials in the
sense of the nanomaterial definition. Many of those are also produced in high
volumes. Examples are salts of silicic acid (e.g. silicic acid, calcium salt
and silicic acid, aluminium sodium salt, other amorphous silica products), silica
fume (by-product of thermal silicon production), fused silica and polymerised
forms of biogenic silica (e.g. from diatomae).[220] 2.3. Titanium dioxide (TiO2,
EC Number 236-675-5) Titanium dioxide powder exists both in bulk[221] and nanoform, as well as in
various crystalline modifications, including rutile and anatase. In its bulk
form, it has been used extensively for about 90 years as the principal white
pigment (maximum reflectivity at around a particle size of 300 nanometres).
Titanium dioxide is also an effective UV filter. The nanoform (around 50
nanometres) is transparent, which provides an esthetic advantage for uses in
sunscreens (mostly rutile). Nanoform TiO2 in the anatase modification
also has specific electrical and photocatalytic as well as antimicrobial
properties. The nanoform of anatase is reported to be more reactive than the
bulk form. The substance titanium dioxide has been registered under REACH.[222]
According to industry, the registration covers all forms of titanium dioxide
including the bulk and the nanoform but with no specific differentiation. The
substance has not been classified as hazardous by the registrant.[223] Results from experimental animal studies
show inflammogenic, oxidative and genotoxic pulmonary responses at high doses.
Chronic exposure also has the potential to promote tumour development.[224],[225] There is also one study showing genotoxic responses after oral
administration in animal studies.[226] Titanium dioxide has been in 2006
classified by the International Agency for Research on Cancer (IARC) as an IARC
Group 2B carcinogen ''possibly carcinogen to humans.[227] US
NIOSH recommended a lower exposure limit for ultrafine particles of titanium
dioxide[228]:
0.3 mg/m3 for TiO2 nanoparticles (<100 nm), versus 2.4 mg/m3 for
fine particles (>100nm), based on the particle surface reactivity. Although
it is established that TiO2 does not pass undamaged skin, there is
an ongoing scientific debate on whether and to what degree TiO2 nanoparticles
can penetrate damaged skin. The approval for use of TiO2 as a UV
filter in sunscreens is currently being updated by SCCS. According to SRI, the global market for
nanoform TiO2 is estimated to be about 10 thousand tonnes per year.
The Commission has also received estimates which are higher than this but still
in the same rough order of magnitude. Around 5 thousand tonnes per year are
used in the personal care industry, of which around 430 tonnes in sunscreens.
Next to sunscreens, the UV filtering properties are also used in coatings for
plastics and metals, varnishes for wood preservation, in textile fibres and in
packaging films. Another main use is catalysts (e.g. decomposing NOx
into nitrates or N2). The photocatalytic and antimicrobial properties
are used in 'self-cleaning' products (e.g. windows, cement, tiles, textiles for
use in hospitals) and air purification systems. Use in tribological coatings
prevent deposits in engines and enhance fuel efficiency. TiO2
nanoparticles are also used to increase scratch-resistance of coatings and in the
production of electronic components and dental impressions. TiO2 can
also be used in dye-sensitized solar cells to produce electricity, though
efficiency is currently lower than traditional silicon solar cells. Workplace exposure can occur at production,
use, when machining materials and from waste and depends on the work procedure
and applied risk management measures. Exposure to
humans and the environment at the use stage varies according to application. It can be high, in particular in
cosmetics applications. In other applications where the nanoparticles are
embedded in a matrix or used in closed systems, it is estimated to be low,
especially if referring to short-term exposure. There are ongoing discussions
whether leaching (e.g. of outdoor paints or release at the waste stage) could
lead to exposure to significant amounts of nanoparticles.[229] 2.4. Zinc oxide (ZnO, EC Number
215-222-5) Like titanium dioxide, zinc oxide powder
exists in bulk and in nanoform. Its nanoform is colourless and an effective
UV-filter with a different spectrum than titanium dioxide. It also has
antimicrobial properties (though less strong than TiO2) and can be
used as an active agent in self-cleaning products. The substance zinc oxide has been registered under REACH.[230]
However, the registration is unspecific to the nanoform (although certain
references could be interpreted as referring to the nanoform). It has been
classified as hazardous (Aquatic Chronic 1) with the following Hazard Statement
(GHS): H410: Very toxic to aquatic life with long lasting effects.[231] SCCS currently assesses ZnO UV filters. Like the bulk form of ZnO, ZnO
nanoparticles show a relatively high toxicity for cells of different tissues
and different organisms in in-vitro studies. For most cell types, the relevant
value is in the range of 10-20 µg/ml. There are limited in-vivo studies on ZnO
nanoparticles indicating severe but temporary pulmonary inflammatory responses.
The effects for nanoscale and fine particles seem to be very similar. Zinc oxide fine particles (e.g. from zinc oxide fume, e.g. in
welding) can cause metal fume fever.[232],[233] According to SRI, the global market for
nanoform zinc oxide is several thousand tonnes per year. Major uses are as a
UV-filter in cosmetics (where it competes with bulk zinc oxide but has the
advantage of being transparent), in varnishes (as a UV-filter and self-cleaning
agent), ceramics and electronics. Nanoform zinc oxide is also used in rubber,
improving toughness, increasing abrasion resistance (e.g. reducing wear loss in
tyres) and preventing UV and bacterial degradation. In this way, the life time
of rubber products can be prolonged. An emerging use is zinc oxide nanowires
for UV nanolasers. Uses are also reported in liquid crystal displays and solar
cells.[234] Workplace exposure can occur at production,
use, when machining materials and from waste and depends on the work procedure
and applied risk management measures. Exposure to
humans and the environment at the use stage varies according to application but can be high in particular in
cosmetics. Another source of environmental exposure is wear of tyres[235]. There are ongoing
discussions whether release at the waste stage could lead to exposure to
significant amounts of nanoparticles. 2.5. Aluminium
oxide (Al2O3, EC Number 215-691-6) Aluminum oxide nanoparticles are widely
used as fillers in polymers and tyres and to increase scratch- and
abrasion-resistance in coatings. The substance aluminium oxide has been registered under REACH[236].
However, the registration is unspecific to the nanoform (although certain
references could be interpreted as referring to the nanoform). It has not been
classified as hazardous.[237]
Aluminium oxide nanoparticles show a low
level of toxicity, although pulmonary inflammatory responses can be observed at
very high doses.[238]
According to SRI, the global market for
nanoform alumina powders is estimated at 200 thousand tonnes, representing a
market value of €750 million. Nanoform Al2O3 powders and
dispersions are used inter alia in scratch- and
abrasion resistant coatings (e.g. for cutting and grinding tools, automobile
exteriors, safety glasses and scratch-resistant windows for barcode scanners,
flooring), as abrasive particles in slurries for
polishing semiconductor and precision optical components, in the coating of
light bulbs and fluorescent tubes, as a flame retardant, as fillers for
polymers and tyres, in coatings of high-quality inkjet papers, in catalysts
including the support structure in automobile catalytic converters, in
refractory materials and as ceramic filtration membranes. Nanoform alumina can
also be used for the manufacture of transparent ceramic bodies for
high-pressure lamps. Workplace exposure can occur at production,
use, when machining materials and from waste and depends on the work procedure
and applied risk management measures. Exposure to humans and the environment at
the use stage is estimated to be rather low as the aluminium oxide is mostly embedded in a matrix and most
applications do not seem to imply an intended release. However, there could be
some exposure e.g. through wear of tools or tyres. There
are ongoing discussions whether release at the waste stage could lead to
exposure to significant amounts of nanoparticles. 2.6. Aluminium hydroxides and
aluminium oxo-hydroxides There are also different aluminium
hydroxide (e.g. bayerite and gibbsite) and aluminium oxo-hydroxide (e.g.
boehmite and diaspore) particles in nanoform. Aluminum hydroxide Al(OH)3
in powder form is used as a flame retardant and as filler in carpets, rubbers,
plastics, and foamed plastics. Moreover, it is used in toothpaste and
cosmetics. Aluminum (hydr)oxides are often used in the dye and plastics
industries as thickeners and fillers and as agents that reduce adhesiveness and
increase scratch resistance. Besides, they serve to enhance the color
saturation of paints and varnishes.[239] 2.7. Iron oxides: Diiron
trioxide (ferric oxide, hematite, Fe2O3, EC Number 215-168-2)
and triiron tetraoxide (ferrous-ferric oxide, magnetite, Fe3O4,
EC Number 215-277-5) There are several types of nanoform iron
oxides. According to SRI, the most common ones are nanoform hematite (ferric
oxide or Fe2O3) and nanoform magnetite (ferrous-ferric
oxide or Fe3O4). The substance diiron trioxide has been registered under REACH.[240]
However, the registration is unspecific to the nanoform (although certain
references could be interpreted as referring to the nanoform). It has not been
classified as hazardous.[241]
The substance triiron tetraoxide has been registered under REACH.[242]
However, the registration is unspecific to the nanoform (although certain
references could be interpreted as referring to the nanoform). It has been
partly classified as hazardous with the following hazard statement (GHS): H251:
Self-heating: may catch fire.[243] Iron oxide nanoparticles show a low level
of toxicity, although production of inflammatory factors observed in some
studies.[244] According to SRI, industry sources believe
that the global market for iron oxide nanoparticles is currently about €20-40
million, which should correspond to roughly 100 tonnes. This value should
however be taken with caution because it is difficult to distinguish between
bulk and nanoform applications of iron oxides. Nanoform ferric oxide particles
are used in pigment applications (e.g. in automotive industry or in cosmetics)
offering clean shades of a number of colours but with high transparency while
still offering protection from UV light. Magnetite particles have been used for
a long time for data storage in magnetic tapes, hard drives etc. There is a
trend to use smaller particles including nanoparticles for these uses. Another
use of magnetite nanoparticles is ferrofluids, which are stable colloidal
suspensions of magnetic nanoparticles in a liquid carrier. Ferrofluids are used
e.g. in electronic components like loudspeakers and hard disks (preventing dirt
particles from entering the hard drive), or in shock absorbers in the
automotive industry. Other emerging applications of nanoform iron oxide
particles are in medicine. After selectively attaching nanoparticles to tumour
cells, those cells can selectively be destroyed by applying electromagnetic
energy. Drugs and diagnostic agents attached to magnetic nanoparticles could
selectively be transported to targets in the body. Other uses of iron oxide
nanoparticles include polishing media, catalysts, components in fuel cells,
oxygen sensors, ceramics and optoelectronic devices, and soil and groundwater
remediation and water treatment. Workplace exposure can occur at production,
use, when machining materials and from waste and depends on the work procedure
and applied risk management measures. Except in medical
applications and cosmetics, exposure to humans and the environment at the use stage is estimated to be rather
low as the iron oxide is mostly embedded in a matrix and applications do not
seem to imply an intended release. There are ongoing discussions whether
release at the waste stage could lead to exposure to significant amounts of
nanoparticles. Specific exposure could also arise in applications for soil and
groundwater remediation as well as water treatment. 2.8. Cerium
dioxide (CeO2, EC-Number 215-150-4) Ceria (CeO2) is a rare-earth
oxide with specific optical properties. The substance cerium dioxide has been registered under REACH.[245]
The registrant has indicated that the substance has a nanoform and has provided
separate information on the nanoform. Neither form has been classified as
hazardous.[246]
Inflammatory responses to cerium dioxide
nanoparticles at high doses have been observed in-vitro for certain cell lines,
though not for others.[247] According to SRI, the
global market for nanoform cerium oxide is around 10 thousand tonnes. Nanostructured CeO2-x films are used in applications in
optical, electro-optical, microelectronic and optoelectronic devices. Nanoform
ceria is used inter alia as a polishing material for glass surfaces and silicon
wafers, to finish photomasks and disk drives, as an anti-corrosion material,
e.g. in exterior architectural paint, steel and other metal plates, and in fuel
cells. Another major application is as a catalytic diesel fuel additive,
decreasing toxic diesel emissions and increasing fuel efficiency. Workplace exposure can occur at production,
use, when machining materials and from waste and depends on the work procedure
and applied risk management measures. Except in
applications as a fuel additive, exposure to humans and the environment at the use stage is estimated to be rather
low. There are ongoing discussions whether release at the waste stage could
lead to exposure to significant amounts of nanoparticles. 2.9. Zirconium dioxide (ZrO2,
EC-Number 215-227-2) Ceramic materials made by sintering
nanoform zirconia (ZrO2) powder have a number of unique properties,
including some forms with very high fracture toughness. The substance zirconium dioxide has been registered under REACH.[248] However, the registration is unspecific to the nanoform. It has not
been classified as hazardous.[249] In vitro tests showed stress on human lung
epithelial cells at high doses.[250] According to SRI, total consumption of
nanoform zirconium dioxide is estimated to be in the range of 2,500-3,000
tonnes. The largest application, with about 50% is in optical connectors,
followed by fuel cells, lithium-ion batteries, catalysts and ceramic membranes.
Other developing applications are in structural and electronic ceramics, dental
fillings, prostheses, fluorescent lighting and as polishing agent. Workplace exposure can occur at production,
use, when machining materials and from waste and depends on the work procedure
and applied risk management measures. Exposure to humans and the environment at
the use stage is estimated to be low, as in most applications it is fixed in a
matrix. An exception is the application in biomedical implants, where wear can
lead to the generation of nanoscale debris. One of the advantages of ceramic
implants is the lower release of wear debris as compared to polymer or metal
components. There are ongoing discussions whether
release at the waste stage could lead to exposure to significant amounts of
nanoparticles. 2.10. Other oxide nanomaterials Other oxide nanomaterials on the market
include barium titanate, barium sulphate, strontium titanate, strontium
carbonate, indium tin oxide (ITO) and antimony tin oxide (ATO). Barium titanate
powders are the dominating raw material for the production of ceramic
dielectric layers in low-temperature multilayer ceramic capacitors (MLCC).
According to SRI, it is marketed in annual quantities of 15000 tonnes globally.
Indium tin oxide is a semi-conducting material used as thin-film material for
the production of transparent electrodes in liquid crystal displays, touch
screens, organic LEDs, thin-film solar cells, semiconducting sensors etc. Due
to its IR-radiation reflectivity it is often used as thermal insulation coating
on window glass. Its anti-static properties make it additionally suitable e. g.
for packing and storage of sensitive electronic components. However, as
ITO-prices have drastically increased due to a global indium production
shortage within the last years, research for alternatives has intensified.
Antimony tin oxides have similar IR-radiation reflectivity properties. Among
these materials, only the substances barium sulphate and strontium carbonate have
been registered under REACH (both unspecific to nanomaterials).[251] They have not been classified
as hazardous.[252]
There are also other similar oxides but less information is available to what
degree these oxides are already on the market. For further oxides which have been
registered under REACH, there is information that nanoforms exist, and certain information in the registration
dossier could be interpreted as referring to the nanoform. These substances include[253]
dibismuth trioxide, nickel monooxide and disilver oxide. There is also information on the existence
of other nanoforms of oxides, e.g. a wide range of rare earth oxides. Most of
those substances, if at all, are marketed only at smaller scale. 2.11. Calcium
Carbonate (CaCO3, EC-Number 207-439-9) Most of the fine-ground calcium carbonate
is generally in a particle size above 100 nm. There are however also nanoforms
of this material, although it is difficult to get a full picture of the use of
the nanoform. It seems that ultrafine calcium carbonate is used as an advanced
filler in sealants and in plastic for window frames.[254] Fine-ground calcium
carbonates are widely used as fillers in paper, plastics, paints and coatings,
and adhesive and sealants. They are also used as a food additive (E 170). In
the latter cases, most of the material used seems however to be in a particle
size above 100 nm. The substance calcium carbonate has been
registered under REACH.[255]
The registrant has indicated that the substance has a nanoform and has provided
separate information on the nanoform. Calcium
carbonate, including its nanoform, has not been
classified as hazardous.[256]
EFSA has recently given a scientific opinion on re-evaluation of calcium
carbonate (E 170) as a food additive.[257]
This opinion, concluded that “the available data are sufficient to conclude that
the current levels of adventitious nanoscale material within macroscale calcium
carbonate would not be an additional toxicological concern".[258] 2.12. Other
non-oxide inorganic non-metallic nanomaterials Substances in this category which have
nanomaterial forms include e.g. aluminium nitride, silicon nitride, titanium
nitride, titanium carbonitride, tungsten carbide, tungsten sulphide. Among those substances, only the substance tungsten carbide has been
registered under REACH.[259] However, the registration is unspecific to
the nanoform. It has not been classified as hazardous.[260] Aluminium
nitride is used in the electronic industry in various particle sizes, including
nanoparticles. Titanium nitride powders with a particle size from nano- to
micrometers are used as additive in the production of wear-resistant sintered
materials. Furthermore it is added to plastics, particularly to PET. TiN nanoparticles
improve the thermal properties of the material and allow increasing the
production output of PET bottles.[261]
The nanoform has been assessed by EFSA[262]
and authorised as a food contact material.[263]
In vitro tests show cytotoxic effects at high doses.[264] Tungsten carbide is used
mainly for hardening the surfaces of cutting tools to improve wear and
temperature resistance. Tungsten carbide nanoparticles are at the barrier to
large-scale production. Tungsten sulphide seems to be a promising lubricant for
harsh conditions. 3. Metals and Metal Alloys[265] 3.1. Gold (Au, EC-Number 231-165-9) According to SRI, the global production of
colloidal gold dispersions in 2010 corresponded to an equivalent to 3.5
kilograms of gold. Gold nanoparticles are mostly used in medical applications,
in particular in in-vitro-diagnostics. Other applications include
catalysts, optics, solar cells, inks for printable electronics, sensors and
surface coatings. Among the few available studies, results on
toxicity of gold nanoparticles seem to be somewhat contradictory but there are
indications of inflammatory responses (in particular for smaller particle
sizes). Gold nanoparticles can become systematically available following
exposure and tend to accumulate in the liver (but to an extent also other
organs).[266] Workplace exposure can occur at production,
use, when machining materials and from waste and depends on the work procedure
and applied risk management measures. Exposure to
humans and the environment at the use stage can be substantial in certain biomedical applications. In most
others, it is estimated to be relatively low because the nanoparticles are
bound in a matrix. There are ongoing discussions whether release at the waste
stage could lead to exposure to significant amounts of nanoparticles. 3.2. Silver (Ag, EC-Number 231-131-3) Nanosized silver was first produced in
1880. It was used for a long time in photographic film applications. Today, it
is mostly used in antimicrobial applications where a high release of silver
ions is needed (in other applications, bulk silver or silver salts are used). The substance silver has been registered
under REACH.[267]
Despite a number of references to tests relating to nanoforms, there is an explicit statement that the nanoform is not covered by the dossier. Silver powder has been classified as hazardous (Aquatic Chronic 1
and Aquatic Acute 1) with the following Hazard Statements (GHS): H410: Very
toxic to aquatic life with long lasting effects and H400: Very toxic to aquatic
life.[268] Silver nanoparticles show various adverse
health effects at high doses. At very high doses, they can provoke pulmonary
oedemas and brown stains in skin and body organs (argyria). There are
indications that silver nanoparticles can penetrate skin, become systematically
available following exposure and tend to accumulate in the liver (but to an
extent also other organs).[269]
Silver is known as a highly ecotoxic metal, in particular for the aquatic
environment. This seems to be linked to the toxicity of the silver ion.
However, there are also studies which show higher effects from silver
nanoparticles than what might be expected from the presence of ions alone.[270] There are also concerns on
the possible development of antimicrobial resistance due to increased use of
nanosilver, as well as possible adverse effects on waste water treatment
processes. The Commission has recently issued a mandate to SCENIHR to assess
safety, health and environmental effects of nanosilver and its role in
antimicrobial resistance.[271] According to SRI, the global market for
nanoform silver in antimicrobial uses is estimated at 22 tonnes (around 10% of total use of silver for
antimicrobial use). Antimicrobial uses of nanoform silver include anti-microbial textiles for hospitals, wound plasters, and
anti-odour sportswear, bed mattresses, socks or underwear. There are also
reported uses in toys, household appliances such as refrigerators and washing
machines, cosmetics, containers for contact lenses, etc. A much lower amount
(in the range of 200 kg) went into non-textile antimicrobial coatings. Other
uses of nanoform silver in small quantities include inks for inkjet printers
and printable electronics, catalysts, photovoltaics, displays and fuel cells. Workplace exposure can occur at production,
use, when machining materials and from waste and depends on the work procedure
and applied risk management measures. Exposure to
humans and the environment at the use stage can be significant for
antimicrobial applications. For other applications, it is considered to be low
because it is bound in a matrix. There are ongoing discussions whether release
at the waste stage could lead to exposure to significant amounts of
nanoparticles. 3.3. Other metallic
nanoparticles Platinum and palladium alloy nanoparticles are mostly used in electronics (production of
multi-layer ceramic capacitors). According to SRI, quantities reported are in
the range of 12 tonnes annually (including sizes above 100 nm). Other uses
include catalysis (including combustion exhaust purification) and energy
technologies. Uses in data storage and medical applications are being
discussed. Copper nanopowders (though mostly in sizes above 100 nm) are used in electronics and,
to a small degree, in inks. Copper nanoparticles are highly toxic to the
aquatic environment.[272] Iron nanoparticles are mostly used in magnetic recording tapes (needle shaped ferrite
particles), though this use is declining. Titanium nanoparticles are increasingly used as an alloy compound in lightweight materials
within the aerospace and increasingly the automotive sector, and as a material
for medical implants.[273] There are also other metal nanoparticles
(e.g. nickel, cobalt, aluminium, zinc, manganese, molybdenum, tungsten,
lanthanum, lithium) used in smaller quantities, e.g. in electronics, though
it is not always clear to what degree the particles are below 100 nm. Rhodium nanoparticles
are reported to be used in catalysts.[274] 4. Carbon-based nanomaterials 4.1. Fullerenes Fullerenes are molecules consisting of an
even number of 60 or more carbon atoms, which form a cage-like fused-ring
polycyclic system with 12 5-membered rings and the rest 6-membered rings (see
http://cdb.iso.org). The simplest molecule with 60 carbon atoms is spherical
with a diameter of around 0.71 nm.[275]
The studies conducted so far suggest
oxidant driven responses in the lungs (inflammation, cytotoxicity and tissue
damage). There are limited ecotoxicological studies which indicate possible
aquatic toxicity. However, some of the results may also be due to the solvents
used.[276] Despite substantial research and
development activities, the current market for fullerenes and derivatives is
supposed to be relatively small, including additives for polymers used in
sports equipment such as tennis rackets and golf balls (strength), cosmetics
(dark color, anti-aging skin creams), in fuel cells, lithium battery anodes, solar
cells component, protective eyewear etc. There is also significant research,
e.g. into medical applications. Workplace exposure can occur at production,
use, when machining materials and from waste and depends on the work procedure
and applied risk management measures. Exposure to
humans and the environment at the use stage can be significant in particular
for cosmetics and biomedical applications. For other applications, it is
considered to be low because it is bound in a matrix. There are ongoing discussions
whether release at the waste stage could lead to exposure to significant
amounts of nanoparticles. 4.2. Carbon nanotubes and
carbon nanofibers[277] Carbon nanotubes are tubes consisting of
one or more concentric sheets of carbon atoms arranged in the same way as the
carbon atoms in ordinary graphite. In the case of single walled carbon
nanotubes, the tube diameter is close to 1 nm. Multi-walled carbon nanotubes
consist of several such tubes in each other (similar to a Russian doll but made
out of tubes). Depending on the structure of the tube, they may exhibit very
high thermal and electric conductivity and a high strength-to-weight ratio. The substance multi-walled carbon nanotubes
has been registered under REACH.[278]. The registrant has indicated
that the substance is a nanomaterial. It has not been classified as hazardous.[279]. There is another
registration of multi-walled carbon nanotubes under graphite.[280] The registrant has indicated
that the substance is a nanomaterial. It has been classified as hazardous with
the following Hazard Statements (GHS): H319: Causes serious eye irritation; and
H335: May cause respiratory irritation.[281] In some studies, lung toxicity
(inflammation, cytotoxicity and tissue damage) was observed after carbon
nanotube exposure. There are indications that there are variations between
different types of carbon nanotubes, with single walled carbon-nanotubes often
being shown to be more toxic than multi-walled carbon nanotubes, and longer
length (> 20µm) resulting in greater pathogenicity. Some animal studies detected that specific modifications of carbon nanotubes showed
effects similar to that of asbestos.[282],[283] Some of the observed effects may also be driven by metal
contaminations. According to SRI, the market of carbon
nanotubes (thinner than 20 nm) worldwide is estimated around 200-250 tonnes (€30-40
million, mostly multi-walled carbon nanotubes) in 2009. The largest use is as a
product imparting electrical conductivity to plastic materials, e.g. in disk
drive components or automotive plastic fuel lines and fenders (electrostatic
coatings). Other uses include polymer additives, paints and coatings, fuel
cells, electrodes, electrolytes and membranes in batteries, especially in
miniature lithium batteries. There is a lot of research and development into
new applications, including into “in-situ component use” which might in term
complement and expand the use of silicon in electronics. According to SRI, the market for carbon
nanofibres in the thickness range between 20 to several 100 nm is estimated at
around 300-350 tonnes (€50-60 million) in 2009. There is a strong increase of
use of nanofibres in lithium ion batteries which is by far the largest
application. Other uses include fuel cells, fabrics for filtration or in
plastic compounds for fuel lines. There are also significantly higher
estimates in terms of marketed volumes of carbon nanotubes, nanofibers,
fullerenes and POSS (around 3500 tonnes annually).[284] Workplace exposure can occur at production,
use, when machining materials and from waste and depends on the work procedure
and applied risk management measures. Measurements of
airborne CNTs in workplaces in research and industrial settings have shown a
likely exposure of workers in some cases. Higher levels of airborne CNTs were
found in particular where processes such as extrusion and cutting of bags
containing nanomaterials, dry-sawing of nanomaterial-containing composites took
place.[285] Exposure to humans and the environment at
the use stage is considered to be low because it is bound in a matrix in most
uses. There are ongoing discussions whether release at the waste stage could
lead to exposure to significant amounts of nanoparticles. Impacts on recycling
are also under investigation. 4.3. Carbon black (EC number 215-609-9) Carbon black is a black powder
consisting of amorphous carbon to a degree of 80-95 %. It is manufactured
by controlled incomplete combustion of hydrocarbons. There are various grades
with different primary particle sizes, most of them between 1 nm and 100 nm
(more than 95% of global production). However, there are also grades with
primary particle sizes up to 500 nm. In industrial materials, the primary
particles are normally aggregated or agglomerated. The substance carbon black has been registered under REACH[286]
(identified in one of three registration dossiers as a nanomaterial using the
relevant tick-box). In one of three registration
dossiers, it has been classified as hazardous (Carc. 2)
with the following Hazard Statement (GHS): H351: Suspected of causing cancer;
Route of exposure: Inhalation. In the other two dossiers, it has not been
classified.[287]
Based on results from experimental studies[288], the International Agency for
Research on Cancer (IARC) of the World Health Organization (WHO) classified
carbon black as a possible carcinogen to humans.[289] Among the few long term epidemiological studies,
there are studies on respiratory health in the carbon black industry.[290],[291] In its assessment of
those studies, the Engineered Nanoparticles - Review of Health and
Environmental Safety (ENRHES) concluded: “The results from the discussed
epidemiology studies of the carbon black industry indicate some adverse effects
of exposure to carbon black dust on respiratory health. However, the main
findings are reassuring in that respiratory symptoms and lung function appear to
be primarily accociated with current exposure rather than being caused by
cumulative exposures. A mortality study by Sorahan et al. 2011 clearly
indicates no strong and little suggestive evidence of excess non-malignant
respiratory disease associated with working in the carbon black industry.
Despite the fact that two of the five factories investigated generated evidence
that there was excess mortality from lung cancer, the study has failed to link
this disease to carbon black exposure.”[292]
IARC[293]
also reviewed those studies, along with a number of other studies.[294] It considered that
epidemiological evidence was inconsistent and therefore concluded that that
there is inadequate evidence from epidemiological studies to assess whether
carbon black causes cancer in humans. [295]
Several authors detected inflammation,
cytotoxicity and tissue damage induced by carbon black nanomaterials in the
lungs as a consequence of carbon black exposure.[296] [297] Some
cardiovascular effects as a consequence of carbon black exposure were also
found.[298] According to SRI, total world consumption
of carbon black was estimated in 2010 at 9.6 million tonnes, with a market
value of around 10 bn €. As filler material carbon black substantially
increases the mechanical wear-resistance of rubber products. Around 73% of the
world production goes into tyres, and another 19% into other rubber products.
Further applications include pigments (toners, printer inks) and antistatic
fillers for plastic packaging. There are also reported uses as mascara, flower
soil, décor paper and fibres, and to manufacture electrodes and carbon brushes.[299] Workplace exposure can occur at production,
for example in rubber and tyre manufacturing, use, from abrasion and from waste
and depends on the work procedure and applied risk management measures. Exposure
to humans and the environment at the use stage varies according to application
but can be significant, e.g. environmental exposure due to wear of tyres.[300] There
are ongoing discussions whether release at the waste stage could lead to
exposure to significant amounts of nanoparticles. 4.4. Graphene flakes Graphene flakes consist of a single-layer
graphite sheet. They became subject of significant research since 2004, when
graphene flakes were isolated through new methods, for which Andre Geim and
Konstantin Novoselov were attributed the Nobel Prize in Physics for 2010. Graphene flakes are a semi-metal or zero-gap semiconductor. They have a very high electron mobility at
room temperature, a high opacity and a number of other properties which makes them
a promising material for a number of applications, even though market
development is still at an early stage. Possible applications are sensors,
graphene transistors, integrated circuits, electrochromic devices, transparent
conducting electrodes, solar and fuel cells, antimicrobial materials, specific
materials for aircraft (e.g. lightning strike protection, prevention of ice
adhesion, radiation hardness) and the automotive industry (e.g. prevention of
static build-up on fuel lines). Exposure to humans and the environment is
estimated to be rather low, as the material is normally fixed in a matrix in
the above applications. Behaviour of graphene flakes at the end-of-life stage
is still unknown. 5. Nanopolymers and Dendrimers There are many nanomaterials
used as an ingredient in polymers. This type of use is described under the
relevant substances above. In addition, there are specific
polymeric nanoparticles, nanotubes, nanofibres, nanofilms and nanostructures.
Polymers are not subject to REACH registration.[301] Dendrimers are a distinct
group with specific polymeric structures. These substances are described below.
Most of these substances are at an early stage of market development described
applications are often still at research and development stage. Sufficiently
robust data on market quantities of marketed substances could not be found. Polymer
nanoparticles are nanoscale polymeric units
such as e. g. polyalcylbenzene-polydiene nanoparticles (PAB-PDM). They are used
e.g. in drug delivery systems or as filler material in matrix composites. Polymer
nanotubes, nanowires and nanorods have
potential applications in electronic, magnetic, optical, optoelectronic, and
micromechanical devices. One of the promising polymeric nanotube types are
polyaniline nanotubes (PANI) which show a good conductivity and may be used for
e. g. conductive fabrics. Polyglycidylmethacrylate
(PGMA) fibres can be utilized to form fabrics
and so called "smart fibres", which change their properties depending
on the environmental conditions. Textiles based on PGMA fibres may switch e. g.
between hydrophobic and hydrophilic, between conductive and non-conductive,
between acidic and basic properties or may change colors etc. Nanocellulose (fibrils and crystals) can be used as a reinforcement material in
composites and for medical implants.[302] Nanostructured
polymer-films are
polymeric nanoscale thin films appearing mainly as polyalcylthiophene-films,
polystyrene-polyethylene oxide (PS-PEO) films or as acrylic glass (Poly(methyl
methacrylate) (PMMA)) films. They are used as coatings in the bio-medical
sector and have the potential to be used also in other sectors. There are also
other nanofilms, e.g. based on styrene-ethylene-butylene-styrene (SEBS). Polyacrylonitrile
nanostructures (PAN) give rise for utilization in semiconductors, solar cells, sensors
and membranes in filters. Their electrical properties are based on a variable
and controllable bandgap for semiconductor use. Dendrimers
are tree-shaped molecular structures similar to polymers. They are
characterised by a high specific surface and, when dispersed, by a non-linear
mass-viscosity relation. They are relatively expensive and there is not much
information about the current market size. Their major applications include
pharmaceuticals, light-emitting diodes and lasers, catalyst carriers,
cross-linking agents in radiation-curable surface coating resin, semi-permeable
membranes, polymer additives and biotechnological applications. 6. Quantum dots Quantum dots are semiconductors
whose electronic characteristics are closely related to the size and shape of
the individual crystal. Typical dots are made of nanomaterials such as cadmium
selenide, cadmium sulfide, indium arsenide and indium phosphide. They are
applied in rather small quantities in computing, biological analysis,
photovoltaic devices, light emitting devices and photodetector devices.[303] The global market for quantum
dots is estimated at around €55 m.[304] 7. Nanoclays Nanoclays are
nanoparticles of layered mineral silicates such as montmorillonite, bentonite,
kaolinite, hectorite, and halloysite. Nanoclays have
uses e.g. as polymer nanocomposites, in paints, inks, greases, and cosmetics
formulations, as a drug delivery vehicle, in waste water treatment[305] and in tyres.[306] The global market for nanoclays has been evaluated at around €150 m.[307] Several substances which also exist as
nanoclay have been registered under REACH. However, the registration dossiers
are generally unspecific to nanoclays. Moreover, according to industry sources,
some of the nanoclays occur in nature and thus are exempt from registration.[308] 8. Nanocomposites There are various types of composites of
nano- and non-nanomaterials. These materials are not separately described here
but mentioned as possible applications of the relevant substances mentioned
above. 9. Other There are reports on the use of nitrogen and
phosphorous compounds in nanoform, used as flame retardents in textile industry
and polyetherketones in nanoforms as anti-sticking coatings of pans.[309] In addition, there are a number of
substances notified under the CLP Regulation which have been identified by the
notifier as nanomaterial through ticking the “nanomaterial” tickbox, for which
little further information could be found on uses of the nanoform. Thise
include manganese dioxide, divanadium pentoxide, dicopper oxide, siloxanes and
silicones (see also Appendix 3). Appendix 3
ECHA Analysis of Information on Nanomaterials retrieved in the ECHA Databases
for REACH Registrations and CLP Notifications received by the end of June 2011 This appendix is based solely on the
content of the databases at the end of June 2011. Any registration or
notification received after this has not been systematically screened for
information on nanomaterials. It is therefore possible that more registrations
and notifications concerning nanomaterials have been received after this date.
For example, two registrations were received for multi-walled carbon nanotubes
at the end of July 2011. Executive Summary The REACH registration and CLP databases
maintained by ECHA were screened for those registrations and notifications that
include information on nanomaterials. This involved doing a free-text search
for “nano” in all machine readable fields in all registration and notifications
stored in the database. In addition all files attached to registrations were
screened. “Nano” was chosen as the definite search-term for the screening as
there is no definition for nanomaterial in REACH or CLP nor guidelines on how
to report information on size for nanomaterials. The use of “nano” by a registrant/
notifier in a relevant context was considered to be an indication that the
dossier may include nanomaterials or nanoforms within the scope of the
registered/notified substance. Screening of the REACH registration
database at the end of June 2011 yielded a list of 78 registered substances
that include information on nanomaterials from the ca. 4,700 substance
registrations stored in REACH registration database. Of these 78, three
substance registrations had explicitly selected “nanomaterial” as the form of
the substance. Two substance registrations included possibly relevant
information but had not selected “nanomaterial” as the form of the substance. Six
substance registrations included “nano” in the description of the registered
substance but where the registrant referred to the substance as being
nano-structured rather than a nanomaterial. Eight specifically excluded
nanoforms from the scope. For the vast majority of substances (59 of the 78
substances listed), “nano” was found solely in the context of read-across from
studies performed on nanoforms of the registered substance and it cannot be
definitely concluded based on the information included in the respective
dossiers whether or not nanoforms are within the scope of the registered
substance. Screening of ca. 3.2 million notifications
stored on the CLP notification database at the end of June 2011 yielded a list
of 18 notifications where “nanomaterial” was selected as the form of the
substance, one of which had included “nano” in both the chemical and EC name
fields. An additional three notifications had included “nano” in the chemical
name field. The list of substances retrieved from the
REACH and CLP databases using this strategy and clearly including nanoforms
within the scope of the substance are reported in Annexes 2 and 3 of this
report. It should be noted that the screening employed will not find those
substances that include nanoforms but where “nano” was not included in any
field of the respective registrations and notifications or in any file attached
to the registrations. However, as registrants and notifiers were encouraged to
use “nano” as the prefix for any composition, analytical data and information
requirement that referred to the nanoform, we are confident that we have
retrieved those substances where registrants/notifiers wished to explicitly
include information on nanoforms. Based on the screening of the databases at
the end of June 2011, it can be concluded that three registered substances from
the REACH registration database that includes ca. 26,000 registrations for ca.
4,700 substances and 18 CLP notifications from the ca. 3.2 million
notifications in the CLP database had selected “nanomaterial” as the form of
the substance in the respective registrations and notifications. One substance
was common to both lists. It should be noted that registrants include
classification and labelling information in their respective registration
dossiers and thus are not required to make a separate CLP notification for that
substance. Thus the CLP notified substances on the list refer to those
substances that are not currently registered by the party making the
notification. The following report describes how ECHA
retrieved information on nanomaterials stored in the ECHA databases for REACH
registrations and CLP notifications. It details the basis for this action and
describes the content of the ECHA databases in terms of what information is
required to be reported according to specific deadlines for the applicable
legislation and the format in which this information is stored. The absence of
specific requirements for nanomaterials in both the REACH and CLP legislations
is also discussed. A detailed summary of the screening strategy undertaken to
retrieve information from the databases is included together with the results. 1. Basis for the compilation of a list of
substances that include information on nanomaterials in the REACH and CLP
databases In 2010, the Commission made an official
request to ECHA for assistance in the preparation of the REACH and CLP aspects
mentioned in the 2nd Commission communication on the Regulatory aspects of
nanomaterials.[310]
The request from the Commission was to compile information on nanomaterial
types and uses, including safety aspects, which has been reported by the
chemical companies either in their registration dossiers submitted under the
REACH[311]
Regulation or in notifications to the Classification and Labelling Inventory
submitted under the CLP Regulation.[312]
This commitment was included in the ECHA workplan for 2011 under main outputs
for “Activity 7: Scientific and technical advice to EU institutions and
bodies: Report compiled for the Commission by 30 June containing information on
registered nanomaterials”. 2. Description of the REACH and CLP
databases held by ECHA ECHA is the responsible EU agency for the
implementation of both the REACH and CLP regulations. The REACH regulation
which came into force on the 1 June 2007 requires manufacturers, importers and
downstream users to ensure that they manufacture, place on the market or use
such substances that do not adversely affect human health or the environment
(Article 1(3) of REACH) and is applicable to substances in whatever size or
form. To comply with the regulation, manufacturers and importers are required
to submit Registration dossiers to ECHA including detailed information on their
substances as defined in the REACH legal text. The CLP regulation obliges
manufacturers, importers and downstream users to classify substances and
mixtures placed on the market. This regulation explicitly requires these
parties to consider the forms or physical states in which the substance or
mixture is placed on the market and in which it can be reasonably be expected
to be used (CLP Art 9(5)) when evaluating the available information for
classification. To fulfil this obligation, CLP notifications including
classification and labelling information defined in the CLP Regulation are
required to be submitted to ECHA. Deadlines for submission of REACH
registration and CLP notification dossiers to ECHA are defined in the
respective regulations and are typically both tonnage and hazard profile
specific. Since 1 June 2008, ECHA has received more
than 26,000 REACH registrations for approximately 4700 distinct substances (7
March 2011) and more than 3.2 million CLP notifications for approximately
109,000 distinct substances (1 April 2011). The tiered REACH registration
deadlines for existing (or phase-in) chemicals mean that the registrations
received by the 1 December 2010 deadline refer to those substances that are
manufactured or imported per legal entity at > 1000 tons per year and those
that are classified as carcinogenic, mutagenic or toxic to reproduction (CMR)
or have a classification R50/53 that are manufactured per legal entity at greater
than 1 and 100 tonne /year respectively. New substances manufactured or
imported after REACH came into force on 1 June 2007 are required to be
registered when their tonnage exceeds 1 ton /year. The requirement to make a
CLP notification by the 3 January 2011 deadline refers to substances placed on
the market at > 1 ton per year and substances classified as hazardous under
CLP and present in a mixture above the concentration limits specified in Annex
I to CLP or in Directive 1999/45/EC which results in the classification of the
mixture as hazardous irrespective of tonnage. These REACH registrations and CLP
notifications are stored in databases maintained by ECHA. ECHA therefore has a
very large repository of registration and notification dossiers that can in
principle provide information on nanomaterials registered or notified and
therefore on the market. Following the request from DG ENTR and DG ENV, ECHA
has searched these received registration and notification dossiers for those
that include information on nanomaterials and this report details the
information found in the dossiers to date. 3. Application of REACH and CLP
requirements for nanomaterials It is important to note that neither the
REACH nor CLP regulations have any specific requirements for registrants and
notifiers of substances that are nanomaterials or nanoforms of a substance nor
is there a definition for nanomaterial in the REACH and CLP regulations. The
European Commission addressed this in a series of papers endorsed by the REACH competent
authorities. In document CA/59/2008 rev.1 “Nanomaterials under REACH”[313], it was clarified that
nanomaterials are covered by the definition of substance under REACH and that
REACH requirements are applicable to nanomaterials even though there are no specific
provisions in the legal text for nanomaterials. It was agreed that
nanomaterials could be considered as either substances in their own right and
thus registered as such or as forms of a substance and included in the
registration dossier of corresponding bulk substance. In both cases, the
respective registration dossier should include all relevant information on the
nanomaterial. The phase-in status of nanomaterials was also addressed and it
was agreed that their status as existing chemicals would depend on the
registration strategy adopted by the registrant; nanomaterial substances are
considered to be phase-in when listed on EINECS and pre-registered
appropriately and nanoforms of a bulk substance are considered to be phase-in
when the bulk substance is listed on EINECS and appropriately pre-registered. For CLP notifications, document CA/90/2009
Rev. 2 “Classification, labelling and packaging of nanomaterials in REACH and
CLP”[314]
states that classification and labelling of nanomaterials should follow the
rules set in the CLP regulation and that it should be done on a case-by-case
basis giving due consideration to relevant available data. It was considered
vital that the notifier evaluates whether changes in size, form or physical
state influence hazardous properties. It was noted that a separate notification
may be required for the nanoform of a bulk substance when the available data on
the intrinsic properties indicates a difference in hazard class. There was therefore the expectation that
the nanoform be reported in the dossier as any other form of the substance
together with information on its hazardous properties and the risk management
measures to handle the risk, whenever appropriate. Registrants and notifiers
were encouraged to make explicit in their dossiers if they believed their
substance was a nanomaterial or a nanoform of a substance. REACH registration dossiers are submitted
in IUCLID format to ECHA. IUCLID refers to the software application that
enables registrants to store data on chemicals and to prepare and submit
dossiers. To aid REACH registrants to include information on nanomaterials in
their dossiers, ECHA prepared a technical IUCLID manual “Nanomaterials in
IUCLID 5.2”[315]
where registrants were provided with practical instructions on the available
IUCLID fields for nanomaterials and on how to ensure that information included
was readily retrievable. For example, the manual highlighted the new specific
fields (picklists) available in IUCLID 5.2 (release data 15 February 2010)
where registrants could select “nanomaterial” as a form of the substance in the
information requirements for “form of the substance” and in the classification
and labelling sections of their dossiers. The manual also provided technical
instructions on how to identity substances as nanomaterials and/or include
nanoforms as different substance compositions in submitted registration IUCLID
dossiers. CLP notifications could be submitted as
IUCLID dossiers or via an on-line tool in REACH-IT. For submissions in either
IUCLID format or via the on-line tool, the option to select nanomaterial was
also available for “form of the substance” under classification and labelling. 4. Summary of the screening strategy for
retrieving information on nanomaterials included in REACH and CLP dossiers The strategy adopted for retrieving
information stored in REACH registrations and CLP notifications was based on
how the information is stored in the respective databases. REACH registration database: REACH registration dossiers are stored in the IUCLID database
maintained by ECHA. Information can be retrieved from the dossiers by ECHA and
member state competent authorities (MSCAs) by IUCLID query tools or via
REACH-IT. For the purpose of this exercise, a combination of standard IUCLID
query tools for retrieving information from IUCLID dossiers and other search
tools developed in-house were used to identify those dossiers that included
information on nanomaterials in any IUCLID text-field or any file attached to
the dossier. The screening strategy for REACH
registration database is summarised as follows: ·
Retrieve those dossiers that selected
“nanomaterial” as form of the substance in the respective fields available ·
Retrieve those dossiers who reported the
nanoform as a separate composition of the substance in the appropriate section
of the dossier ·
Free-text searching of all fields in all IUCLID
dossiers in the ECHA IUCLID database ·
Free-text searching of all files attached to all
IUCLID dossiers in the database (files attached include the CSR, analytical
information relevant for substance identification and any other relevant
information the registrant wishes to include to fulfil an information
requirement) The four screening steps were undertaken
independently of each other and the lists of substances retrieved were
cross-correlated with each other. The implications of the obligation to submit
a joint REACH registration per substance and based on tonnages/hazard class are
briefly outlined in Annex 1 as this determines how information is stored in the
database and when such information is available to ECHA. CLP notification database: all CLP notifications received are stored in the REACH-IT database
and can be screened using IT tools developed specifically for this purpose. The screening strategy for the CLP
notification database is summarised as follows: ·
Retrieve those notifications that selected
“nanomaterial” as form of the substance in the specific field available for
this purpose ·
Free-text searching of all searchable fields in
the notifications (i.e. mainly substance identity-related fields) Choice of search term: “nano” was chosen as the definite search-term for screening for
information on nanomaterials/nanoforms of a substance in registration and CLP
dossiers. As there is no definition for nanomaterial in REACH or CLP nor
guidelines on how to report in the dossiers information on size for
nanomaterials, this ruled out using the information on size as the sole
criterion for screening for those dossiers that refer to
nanomaterials/nanoforms. The use of “nano” by a registrant was considered to be
an indication that the dossier may include nanomaterials or nanoforms within
the scope of the registered substance and led to further analysis of the
dossier. Strengths and weaknesses of the
screening strategy: An obvious weakness of the
strategy is that where a registrant did not use the word “nano” to refer to a
nanomaterial substance or nanoform of a substance included in the scope of the
registered substance, such dossiers would not be found. However as registrants
were encouraged to include information on nanomaterials and in particular to
use “nano” as the pre-fix for any composition, analytical data, information
requirement that referred to the nanoform as detailed in the technical manual
on how to include information on nanomaterials in IUCLID6, it is likely that
where “nano” was not included in the dossier (1) the registrant did not
consider or was not, in the absence of regulatory definition of nanomaterial,
able to determine whether his substance was a nanomaterial/nanoform, (2)
nanoforms were not within the scope of the registered substance or (3) the
absence was due to the voluntary nature of the 'nano' information. Thus, the
inclusion of “nano” in a nanomaterial relevant context in the dossier was
assumed to be an indication that the registrant wished to explicitly address
nanomaterials/nanoforms in the dossier. 5. Summary of the outcome of the screening
process From the searches undertaken of the REACH
registration database at the end of June 2011, it can be concluded that 78
substances out of the ca. 4700 substances on the REACH registration
database included some information on nanomaterials in the dossiers. From screening the ca. 3.2 million
notifications in the C&L database at the end of June 2011, it can be
concluded that 21 notifications had included some information on nanomaterials.
6. Conclusions It should be noted that the screening
employed does not find those substances that may include nanoforms if the key
word “nano” was not included in any field of the respective registrations and
notifications or in any file attached to the registrations. However, as
registrants and notifiers were encouraged to use “nano” as the pre-fix for any
composition, analytical data and information requirement that referred to the
nanoform, we are confident that we have retrieved those substances where
registrants/notifiers wished to explicitly include information on nanoforms. From the searches undertaken, it can be
concluded that 78 substances out of the ca. 4700 substances on
the REACH registration database included some information on nanomaterials in
the dossiers. Out of these 78 substances: ·
3 substances could be considered to have included nanoforms within the scope of
the registered substance: these
registrations had nanomaterial selected as the form of the substance in the available picklists. Note however that there
were 3 separate submissions for one of the picklist substances and only one of
these submissions had nanomaterial selected as the form of the substance. The
other two submissions included “nano” in the description of the substance where
it was considered as a nanostructured material. The
substances are listed in Annex 2. ·
2 substances
included possibly relevant information but a nanomaterial had not been selected
as the form of the substance. ·
6 dossiers
included “nano” in the description of the substance but referred to the
substance as being nano-structured rather than a nanomaterial. ·
For the vast majority of substances listed based
on the REACH registrations (59 of the 78 substances listed), “nano” was
found solely in the context of read-across where there was no evidence that
nanoforms are within the scope of the registered substance but extensive
read-across from studies conducted on nanoforms of the same or analogue
substances were included in the dossier to fulfil specific REACH information
requirements. ·
A further 8 substances also used
extensive read-across from studies conducted on nanoforms of the substance or
analogue substances but where it was explicitly stated that nanoforms were not
within the scope of the registered substance. From screening the C&L notification
database, it can be concluded that 18 notifications out of the ca. 3.2
million received included nanomaterial as the form of the notified substance.
Free text searching of the name fields yielded an additional three
notifications that had included “nano” in a relevant context in the chemical
name field. One of the notifications where the picklist had been selected also
included “nano” in both the chemical and EC name fields. It should be noted
that for those substances that were registered by the REACH 2010 deadline, the
C&L information is typically included in REACH registration dossiers and
therefore a separate notification is not required. Thus, for a given substance,
the parties that registered and notified are different. The substances
retrieved are listed in Annex 3. The list based on REACH registrations
includes many of the substances on the OECD Working Party on Manufactured
Nanomaterials (WPMN) list of representative nanomaterials (Cerium dioxide,
aluminium oxide, iron oxide, zinc oxide, silica, titanium dioxide, silver,
nanoclays, carbon black).[316]
It should however be noted that some of the registrations explicitly exclude
nanoforms from the scope of the registered substance but read-across from
studies conducted on the nanoform to fulfil specific REACH information
requirements. Others refer to studies conducted on nanoforms but do not
explicitly state whether or not nanoforms are within the scope of the
registered substance, while other stated that the substance was nanostructured
rather than a nanomaterial. It is also interesting to consider why
certain substances were not found. An obvious reason that certain substances
like fullerenes were not found from either database is that the tonnages
manufactured and imported are below the tonnage triggers for the
registration/notification deadlines and it is not classified as CMR, R50/53 or
classified as hazardous under CLP. In some cases it may have been unclear to
registrants and notifiers whether or not their substance should be regarded as
a nanomaterial/nanoform. For example, although many inorganic pigments were
registered by the 2010 deadline, very few pigments are included on the REACH
registration based list. It is understood that inorganic pigments exist in
grades that would have a fraction under the 100 nm cut-off that is widely used
to discriminate between bulk and nanoforms. However, there is no consensus of
what “particle” refers to in terms of the interpretation of the 100 nm cut-off.
In addition, different methods for measuring particle size can yield vastly
different values. Also there was no information available on how registrants
should interpret the nano-status of substances that have particle size
distributions with size fraction below 100 nm cut-off or whether the
appropriate metric for reporting the particle size distribution should be mass
or number based. However many of the substances on the C&L based list are
pigments. Annex 1:
REACH requirements in terms of one registration per substance and the
tonnage/hazard triggers that determine when a registration dossier shall be
submitted. Joint registration: REACH applies to substances and all REACH registrants
of the same substance are required to submit certain information jointly to the
Agency (Art (11) of REACH). Other information is company specific and thus to
be submitted for each registrant. From a technical perspective, this means that
only one joint registration dossier is submitted for each substance. This joint
registration dossier is split in a joint and individual (company specific)
parts. This has implications on what information is retrievable from dossiers. In a joint registration dossier,
registrants of the same substance organise themselves such that a lead
registrant submits certain information on behalf of all members of the joint
registration (in the joint part of the registration dossier). Other – typically
company specific – information is contained in the individual (registrant
specific) parts of the joint registration. In some cases, registrants may also
choose to submit information which would normally be submitted in the joint
part in the individual part of their dossier, if these registrants have
confidentiality or cost related concerns or disagree with the lead registrant
on the selection of information. The scope of the registered substance may
thus be defined by the members of the joint registration to include or exclude
particular forms or compositions of the substance registered. This may or may
not be explicitly stated in the dossiers. Normally, the lead registrant submits
all the required physico-chemical, eco-toxicological and toxicological
information required by REACH for that substance. There is also a possibility
to submit the joint chemical safety report (CSR) on behalf of all registrants.
This information is required to be applicable to all forms/compositions of the
substance registered by all members of joint registration. However, as
explained above, there may be cases where this information is contained in the
individual part of the dossier. Thus, in terms of retrieving those dossiers
from the database that include substance specific information on nanomaterials,
registrant specific information on substance identity, manufacture, uses and
exposure is reported in all dossiers received for that substance while
physico-chemical, eco-toxicological and toxicological information is typically
reported exclusively in the lead registrant dossier. Tonnage triggers: It is also important to note that although
registrants of the same substance are required to submit jointly, they are only
obliged to do according to the tonnages as manufactured/imported by their legal
entity. For example, for a non-CMR, non-R50/53 substance, only those
manufacturers/importers that are at or above the 1000 ton/yr trigger were
required to register by the 2010 deadline. Manufacturers/importers with
tonnages below 1000 tons/yr could also register by 2010 but are not required to
do so. The registration deadlines for lower tonnages are 2013 (100-1000
tons/yr) and 2018 (1-10 tons/yr). Manufacturers/importers below 1 ton/yr do not
have an obligation to submit a registration dossier for the substance. This has
the direct implication that registrations received by the 2010 and thus stored
in the ECHA database refer typically to those substances manufactured/imported
≥ 1000 tons per year per legal entity or those CMR substances that are at
or above 1 ton/yr per legal entity or those R50/53 substances that are at or
above 100 ton/yr per legal entity. Annex 2:
List of publicly available substances where information on nanomaterials was
included in REACH registration dossiers received by the end of June 2011. Note this list does not imply that the
nanoform has been registered but solely reports the context in which
nano-relevant information was included in the respective registration dossier
received by ECHA for these substances. Only those substances that clearly
included nanoforms within the scope of the substance are included. Main context where nanomaterial relevant information was retrieved || EC / list number || Substance name || Section where "nano" indicated/found by free-text search Nanomaterial selected as the “form of the substance” || "Nano" appears in public name/ chemical name || composition name/ composition description || Context where "nano" found in the phys-chem, eco-tox and tox IUCLID sections registrant explicitly included nanoforms within the scope of the registered substance || 207-439-9 || calcium carbonate || 2.1 || chemical name and public name || both || Nano-composition 215-150-4 || cerium dioxide || 2.1 || || both || Nano-composition 215-609-9 || Carbon Black || 4.1 || || || Read-across Annex 3:
Compiled public list of substances where information on nanomaterials was
included in C&L notifications received by the end of June 2011. Substance name || EC / list number || CAS number || Chemical name || Nanomaterial selected as the form of the substance || "nano" included in the chemical name || "nano" included in the EC name field of the notification Manganese dioxide || 215-202-6 || 1313-13-9 || || x || || Nickel monoxide || 215-215-7 || 1313-99-1 || || x || || Zinc oxide || 215-222-5 || 1314-13-2 || || x || || Zirconium dioxide || 215-227-2 || 1314-23-4 || || x || || Divanadium pentaoxide || 215-239-8 || 1314-62-1 || || x || || Dicopper oxide || 215-270-7 || 1317-39-1 || || x || || Anatase (TiO2) || 215-280-1 || 1317-70-0 || || x || || Rutile (TiO2) || 215-282-2 || 1317-80-2 || || x || || Carbon black || 215-609-9 || 1333-86-4 || || x || || Aluminium oxide || 215-691-6 || 1344-28-1 || || x || || Strontium titanium trioxide || 235-044-1 || 12060-59-2 || Strontium Titanate(SrTiO3) || x || || Titanium dioxide || 236-675-5 || 13463-67-7 || || x || || Titanium nitride || 247-117-5 || 25583-20-4 || || x || || 617-568-6 || 617-568-6 || 844491-94-7 || Silica, [[dimethyl[2-methyl-3-(methylamino)propyl]silyl]oxy]-and[(trimethylsilyl)oxy]-modified || x || || Appendix 4
List of effects and property improvements through nanotechnologies Examples of the effects and property
improvements through nanotechnologies[317]
Functionality || Application Examples Electronical/Electrical || • Electrically conductive polymers through integration of carbon nanotubes into the – Conductivity || polymer matrix for antistatic applications and electromagnetic shielding. – Dielectric layers || • Improved high-temperature superconductivity through nanoscaled substructures – Superconductivity || for increased ampacity and cost-efficient sol-gel-materials for layer production. – Thermoelectricity || • More efficient thermoelectrics for power conversion of heat through nano- – Electrochemical energy storage || structured semiconductor connections. || • Nanoporous “low-k“-layers for the reduction of delay in conduction in CMOS-circuits Chemical || • Antifogging effect through super-hydrophilic titanium dioxide nanocoatings for – Super-hydrophilicity || glasses and exterior mirrors of cars. – Super-hydrophobicity || • Dirt-repellent coatings, inter alia, through nanoparticle-modified fluor-siloxane/ – Corrosion protection || silane coating agents for textiles, furnishings and façade surface finishings. – Catalysis || • Fire-protection windows on the basis of transparent, nanoparticular fire-protection – Flame protection || gels and layers, which, under the impact of heat, form ultra-fine gas bubbles with – Fire protection || strongly heat-insulating effect. – Adsorption power || • Flame-inhibiting effect for plastic casings and cables through integration of cataly- – Adhesion power || tic nanoparticles in the polymer matrix, which prevent the spreading of flames by – Dissolving power || accelerated formation of non-combustible carbonization residues. || • Anti-fingerprint layers for stainless steel and metal surfaces on the basis of thin glass coatings || • Efficient adsorbent materials for gas storage or for the removal of contaminants through extended active surfaces and adjustable pore sizes Thermal || • Nanostructured heat-protection layers and alloys for turbine materials to achieve – Heat protection || better energy conversion rates at increased working temperatures. – Heat insulation || • Superinsulating nanofoams (aerogels, polymer foams) for heat insulation in buildings – Heat conduction || and industrial processes. – Heat storage || • Better heat conduction through nanofluids and nanocomposite materials on CNT- basis in industrial processes or in solarthermics || • Efficient heat storage through micro/nanoencapsulated phase change materials to be integrated in the facade components. Magnetic || • Nanocrystalline, magnetically soft iron alloys capable of having extraordinary – Magnetically soft materials || magnetic properties impressed on them, inter alia for high-capacity components in – Magnetoelectronics || grids (e.g. toroidal tape core, transformers, choke coils). – Magnetorheology || • Magnetic layer stacks with giant magnetoresistance properties for magneto- – Magnetic induction heat || electronic sensors and data memories. || • Dispersions of surface-stabilized nanoscaled iron particles (ferrofluids) with magnetically controllable viscosity for sealings, shock absorbers etc. || • Iron oxide nanoparticles for heat generation by means of alternating electro- magnetic fields (e.g. for switchable adhesives or hyperthermal cancer therapy. Biological || • Antimicrobial equipment of plastics in medical engineering, furniture surfaces, – Antimicrobial effect || textiles, through silver nanoparticles. – Bioavailability || • Higher bioavailability of medical agents and dietary supplement substances – Biocatalytics || through liposome encapsulation and nanoemulsions.[318] – Moleculare recognition || • Nanoparticles as carriers for the introduction of genetic material into cells – Biocompatibility || (gene vectors) in gene therapy. – Cell permeability || • Molecular recognition of diseased cells for effective drug delivery through surface functionalized drug-delivery systems. || • Nanostructured implant surfaces and nanoparticular bone substitute materials for increased biocompatibility in regenerative medicine. || • Nanostructured templates and carrier substances for efficient biocatalysts. Appendix 5
EU funded research in Nanosafety The European Commission has started funding
projects addressing specifically nanosafety since the 5th EU
Framework Programme for Research and Technological Development (FP5, 1998-2002).
Nanosafety is strategically addressed since the beginning of FP6, with a
regular annual budget increase, from 800 k€ in 2004 to 30 M€ in 2010.
Globally, from 2004 to 2010, FP6 and FP7 projects dedicated to nanosafety
issues represented a total investment of 185 M€ (of which 130 M€ from
the framework programme budget). The framework programme calls are conceived
to cover all aspects necessary for the risk assessment and risk management of nanomaterials:
physico-chemical characterisations of nanomaterials, fate and behaviour in
biological and environmental media, bio-nano interactions, nano-toxicity and
nano-ecotoxicity, life cycle analysis of nanomaterial-embedded products
(including recycling and final treatment), measurement devices, exposure,
worker protection, risk assessment tools and risk management strategies. These European projects are aimed at
closing the knowledge gaps required for the assessment and development of
relevant regulation founded on scientific knowledge. While the research is not
aimed at producing regulatory assessment data for any specific nanomaterial
currently in the market place, all projects have part of their activities that
are specifically dedicated to dissemination of the project's results to
stakeholders and general public. These activities include workshops such as the
joint JRC/ENPRA stakeholders' workshops (www.enpra.eu),
publications in peer-reviewed journals and public reports. A good example of a public
report was produced by the FP7 ENRHES[319]
project which performed a comprehensive and critical scientific review of the
health and environmental safety of fullerenes, carbon nanotubes (CNTs), metal
and metal oxide nanomaterials (http://ihcp.jrc.ec.europa.eu/whats-new/enhres-final-report).
Participants to these European projects also often contribute to more
regulatory oriented activities, such as the RIP-oNs studies and the OECD-WPMN
work, or even sit in scientific committees such as SCENHIR, ensuring therefore
that the knowledge produced in the projects be transmitted. As an exception to the above, a topic
addressing "Regulatory Testing" is planned for 2012 calls. The
objective of the call is to provide legislators with a set of tools for risk
assessment and decision making for the short to medium term, by gathering data
and performing pilot risk assessment, including exposure monitoring and
control, for a selected number of nanomaterials used in products. The outcomes
of the project should also feed the work of the OECD-WMPN. A 10 M€ EC
contribution is planned and a leverage effect from 3 to 5 times is expected
from Member States and industries. Finally, the EU NanoSafety Cluster is a DG
RTD initiative to maximise the synergies between projects addressing all
aspects of nanosafety including toxicology, ecotoxicology, exposure assessment,
mechanisms of interaction, risk assessment and standardisation. The NanoSafety Cluster
comprises 31 projects funded under FP7 and five projects funded under FP6. Additionally,
national projects may contribute to the overall aims of the Cluster. The main
objectives of the NanoSafety Cluster are: to facilitate the formation of a
consensus on nanotoxicology in Europe ; to provide a single voice for
discussions with external bodies ; to avoid duplicating work and improve
efficiency ; to improve the coherence of nanotoxicology studies and harmonize
methods ; to provide a forum for discussion, problem solving and planning
R&D activities in Europe ; and to provide industrial stakeholders and the
general public with appropriate knowledge on the risks of nanoparticles and
nanomaterials for human health and the environment. The NanoSafety Cluster also
delivers yearly a compendium of all its projects, which includes consortia
compositions, projects objectives and results. The last edition can be found
at: www.nanosafetycluster.eu. Appendix 6
Nanomaterials and worker protection: Main publications and websites 1. EU-OSHA[320] references to
nanomaterials use at the workplace: ·
Report - Expert forecast on emerging chemical
risks related to occupational safety and health (2009) http://osha.europa.eu/en/publications/reports/TE3008390ENC_chemical_risks/view
EU-OSHA has published a series of expert
forecasts providing an overview of the potential emerging risks in the world of
work (physical, biological, psychosocial and chemical risks). Among the top ten
emerging risks, three have in common their physico-chemical state as insoluble
particles or fibres: nanoparticles and ultrafine particles, diesel exhaust, and
man-made mineral fibres. The experts agreed that nanoparticles and ultrafine
particles pose the strongest emerging risk. ·
Literature review - Workplace exposure to
nanoparticles (2009) http://osha.europa.eu/en/publications/literature_reviews/workplace_exposure_to_nanoparticles/view
This report focuses on the possible adverse health
effects of workplace exposure to engineered nanomaterials and possible
subsequent activities taken to manage the risk. In order to provide a broad
overview, information from different sources such as scientific literature,
policy documents, legislation and work programs were collected. Documents from
the EU were given priority, although national and international activities have
also been described. Studies published up to November 2008 have been considered
in the report. As the conclusion of this review, the following topics
were identified as priorities for future actions and activities: –
identification of nanomaterials
and description of exposure –
measurement of exposures to
nanomaterials and efficacy of protective measures –
risk assessment of nanomaterials
in line with the current statutory framework –
in vivo studies for assessment of
the health effects of nanomaterials –
validation of the in vitro
methods and methods of physico-chemical properties as methods to determine
health effects –
training of workers and practical
handling guidelines for activities involving nanomaterials in the workplace. ·
Literature review – Risk
perception and risk communication with regards to nanomaterials in the
workplace (2012) http://osha.europa.eu/en/publications/literature_reviews/risk-perception-and-risk-communication-with-regard-to-nanomaterials-in-the-workplace/view This review found that communication on nanomaterials is still poor, with
a majority of Europeans not knowing what nanotechnology is. Even in workplaces
where manufactured nanomaterials are found, the level of awareness is low. For
example, 75% of workers and employers in construction are not aware they work
with them. There are some initiatives to communicate the risks of manufactured
nanomaterials and how to manage these (though not always targeted at the
workplace), for example by major producers, some trade unions, national
dialogues within some Member States, and Europe-wide through the Communication
Roadmap by the European Commission. But much more still needs to be done
(preferably jointly by policymakers, the social partners, national occupational
safety and health bodies, public health agencies, sectoral associations, etc.)
as poor risk communication may generate confusion and lead to unjustified fears
or to underestimation of the risks, with consequent inadequate risk prevention.
Risk communication strategies need to help employers make informed decisions
about their workplaces and put adequate prevention measures in place, and to
empower individual workers to take personal control of their own situations in
order to protect themselves adequately. ·
Database of company Good Practice
on the management of risks from nanomaterials in the workplace http://osha.europa.eu/en/practical-solutions/case-studies/index_html/practical-solution?SearchableText=&is_search_expanded=True&getRemoteLanguage=en&keywords%3Alist=nanotechnology&nace%3Adefault=&multilingual_thesaurus%3Adefault=&submit=Search EU-OSHA
has developed an on-line database of company Good Practice examples of good
workplace management of manufactured nanomaterials which covers a variety of
industries, such as textile, construction and medical applications, in
different EU Member States. ·
A number of useful links
are also available in the agency´s “Useful links” section “dangerous substances and new
technologies” Further to these EU-OSHA publications and the sources
referenced in the bibliography list of these reports, a number of publications
and references with relevance to occupational health and safety and the
priorities identified in EU-OSHA studies are listed below: 2. EU Member States AUSTRIA ·
The Austrian Nanotechnology Action Plan
(available in English at http://www.umweltnet.at/filemanager/download/60006/
) identifies needs for action and formulates recommendations related to, among
others, worker protection ·
Institut für Technikfolgen-Abschätzung, ITA
(Institute of Technology Assessment of the Austrian Academy of Sciences) ·
Nanotrust project http://nanotrust.ac.at/nano.ita.en/index.html
·
Nanotechnologies – nanotextiles, voluntary
agreements in industry (2010) http://osha.europa.eu/en/news/nanotechnologies-2013-nanotextiles-voluntary-agreements-in-industry
·
Nanotechnologies - Assessment of nanosilver
products (2010) http://osha.europa.eu/en/news/nanotechnologies-assessment-of-nanosilver-products ·
Neurotoxicity of
nanoproducts http://osha.europa.eu/en/news/nanotechnologies-neurotoxic-effects-of-nanomaterials ·
Austrian Labour Inspectorate: has a section
on nanomaterials on its webpages, in German only: http://www.arbeitsinspektion.gv.at/AI/Arbeitsstoffe/nano/default.htm.
Also includes the results of case studies of companies working with
nanomaterials, performed in 2009: http://www.ppm.at/downloads/umgang_mit_nano_im_betrieb.pdf. The Austrian Labour Inspectorate is also currently
working on guidelines for the safe use of nanomaterials at the workplace. GERMANY ·
German Government Nano Initiative Action plan
- also includes worker protection. Action Plan 2015 only in German; Action Plan
2010 also in English, available at: http://www.bmbf.de/de/nanotechnologie.php
·
Bundesanstalt für Arbeitsschutz und
Arbeitsmedizin, BAuA (German national institute for
occupational safety and health): ·
Literature overview 2008-2010 related to the use
of nanotechnologies and occupational safety and health, in German: http://www.baua.de/de/Bibliothek/Informationsdienste/Nanotechnologie.pdf?__blob=publicationFile&v=3
·
BAuA also provides a dedicated webpage with
national actions, research and codes of practice, as well as information on the
use of nanotechnologies and exposures to nanoparticles in practice. A selection
of documents is translated into English. See http://www.baua.de/cln_137/de/Themen-von-A-Z/Gefahrstoffe/Nanotechnologie/Nanotechnologie.html
for the German version and http://www.baua.de/cln_137/en/Topics-from-A-to-Z/Hazardous-Substances/Nanotechnology/Nanotechnology.html
for the English version. ·
Among others, BAuA funded a project aiming at
developing a portable device to measure airborne nanoparticles in the
workplace (performed by IUTA, Duisburg – ended 2010). BAuA has now started
to perform workplace measurements of airborne nanoparticles in the industry:
(in German) http://www.baua.de/de/Themen-von-A-Z/Gefahrstoffe/Nanotechnologie/pdf/Forschung-Entwicklung.pdf?__blob=publicationFile&v=7
·
Elaborated by BAuA and the Association of
chemical industries (Verband der Chemischen Industrie, VCI): “Guidance for
handling and use of nanomaterials in the workplace” (2007): http://www.baua.de/cae/servlet/contentblob/717966/publicationFile/48357/guidance.pdf
·
Institut für Arbeitsschutz der Deutschen
Gesetzlichen Unfallversicherung, IFA (Institute for Occupational Safety and
Health of the German Social Accident Insurance): Webpages on nanomaterials and
OSH, including information on workplace measurement, risk assessment and
prevention measures, in English (http://www.dguv.de/ifa/en/fac/nanopartikel/index.jsp
) and in German (http://www.dguv.de/ifa/de/fac/nanopartikel/schutzmassnahmen/index.jsp
) ·
Berufsgenossenschaften der Bauwirtschaft, BG-Bau
(German statutory insurance for the construction sector): ·
Product list of nano-containing construction and
cleaning products: http://osha.europa.eu/en/news/DE-nanoparticles-construction-cleaning ·
The list was up-dated list in 2011: http://www.bgbau.de/d/pages/praev/fachinformationen/gefahrstoffe/nano/PDF-files/nano-liste.pdf
·
Hessisches Ministerium für Wirtschaft, Verkehr und
Landesentwicklung (Hessen Ministry of Economy, Transport and Development): Guidance
on the safe use of nanomaterials in the varnish and paint industry (2009)
in German only: http://www.hessen-nanotech.de/mm/Betriebsleitfaden_NanoFarbeLacke_Vorab.pdf
·
Roller, M (Advisory Office for Risk Assessment,
Dortmund) “Carcinogenicity of inhaled nanoparticles”, Inhalation
Toxicology, 2009; 21(S1): 144–157 FRANCE ·
French Ministry of Labour: Plan Santé au
Travail 2010-2014 (Plan for health at work): http://www.travailler-mieux.gouv.fr/IMG/pdf/PST_2010-2014.pdf Sets up objectives with regards to nanomaterials
and worker protection: ·
Develop health surveillance of workers exposed
to nanomaterials ·
Strengthen the efforts to identify workplace
exposure scenarios and characterise exposure in order to develop adequate
measurement tools and methods ·
Support EU level initiatives to implement legislative
measures on traceability of nanoparticles ·
Improve information to workers likely to be
exposed to nanomaterial containing waste. ·
Called on the French National Agency for Food,
Environment and Occupational Health and Safety ANSES to draft a Good Practice
guide on nanomaterials in the workplace in 2010 building upon the 2008 report
“Nanomaterials – Safety at work” (http://www.afsset.fr/upload/bibliotheque/258113599692706655310496991596/afsset-nanomateriaux-2-avis-rapport-annexes-vdef.pdf) ·
Agence nationale de sécurité sanitaire, de
l’alimentation, de l’environement et du travail, ANSES (French National Agency
for Food, Environment and Occupational Health and Safety): New specific Control-Banding
tool for nanomaterials http://osha.europa.eu/en/news/fr-new-specific-control-banding-tool-for-nanomaterials-developed-by-anses ·
French national public debate on the general options on
the development and regulation of nanotechnologies « Débat public sur les
options générales en matière de développement et de régulation des
nanotechnologies » http://www.debatpublic-nano.org/debat/debat_public.html NETHERLANDS ·
The Stoffenmanager Nano ModuleNano (2011): Adaptation of the Dutch occupational risk assessment tool for
workplace dangerous substances (“Stoffenmanager”) to nanomaterials. Available
at: http://nano.stoffenmanager.nl/Default.aspx
·
Delft University of Technology (TU Delft), in
cooperation with the Lawrence Livermore National Laboratory (USA): Paik, S.,
Y.& Zalk, D. M., Swuste P., “Application of a Pilot Control Banding Tool
for Risk Level Assessment and Control of Nanoparticle Exposures”, Ann. Occup. Hyg., Vol. 52, No. 6, pp. 419–428, 2008 http://annhyg.oxfordjournals.org/content/52/6/419.full.pdf+html ·
TU Delft, “Nanosafety Guidelines.
Recommendations for research activities with ‘free nanostructured matter’”, 2008:
www.veiligheidskunde.nl/xu/document/cms/streambin.asp?requestid=43531312-6BA0-400D-B916-7562D0EEBDE3
·
Social and Economic Council of the Netherlands
(SER), “Nanoparticles in the Workplace: Health and Safety Precautions”.
Advisory Report. Working Conditions Committee. 2009. www.ser.nl/en/publications/publications/2009/2009_01.aspx
SPAIN ·
Instituto Nacional de Seguridad e Higiene en el
Trabajo, INSHT (National Institute for Safety and Hygiene at Work): “Risk
level assessment of nanoparticle exposure by control banding” in Spanish
only: http://www.insht.es/InshtWeb/Contenidos/Documentacion/FichasTecnicas/NTP/Ficheros/821a921/877w.pdf
·
Instituto Sindical de Trabajo, Ambiente y Salud,
ISTAS (Trade Union Institute for Work, Environment and Health): Web pages on
nanomaterials, with practical information on measurement, risk assessment and
control measures, in Spanish only: http://www.istas.net/web/index.asp?idpagina=3332
UNITED KINGDOM ·
Health and Safety Executive: ·
Websection on nanomaterials
http://www.hse.gov.uk/nanotechnology/index.htm?ebul=hsegen&cr=8/31-jan-11 ·
In particular, on fire and explosion properties
of nanopowders (2010) http://osha.europa.eu/en/news/uk-2013-new-hse2019s-report-on-fire-and-explosion-properties-of-nanopowders ·
British Standards Institute, BSI: ·
“Nanotechnologies – Part 2: Guide to safe
handling and disposal of manufactured nanomaterials.”, 2007: http://www.bsi-global.com/en/Standards-and-Publications/Industry-Sectors/Nanotechnologies/PD-6699-2/Download-PD6699-2-2007/ ·
“Guidance on the labelling of
manufactured nanoparticles and products containing manufactured nanoparticles”,
2007: http://www.bsigroup.com/upload/Standards%20%26%20Publications/Nanotechnologies/PAS130.pdf ·
Institute of Occupational Medicine (IOM): “Safenano”,
an initiative designed to help industrial and academic communities to quantify
and control the risks to their workforce, as well as to consumers and the
environment. The website includes a publication database, and some guidance
e.g. on workplace risk assessment. http://www.safenano.org/Home.aspx
3. Other countries SWITZERLAND ·
State Secretariat for Economic Affairs SECO, “Safety
data sheet (SDS): Guidelines for synthetic nanomaterials”, 2010: http://www.seco.admin.ch/dokumentation/publikation/00009/00027/04546/index.html?lang=en&utm_source=oshmail&utm_medium=email&utm_campaign=oshmail-104 ·
Swiss Accident Insurance Fund SUVA:
“Nanoparticles in the workplace” (2009), in German only, includes information
on health effects, workplace measurement, risk assessment and management: http://www.suva.ch/startseite-suva/praevention-suva/arbeit-suva/gefahren-filter-suva/gesundheitsgefaehrdende-stoffe/gs-nanopartikel/nanopartikel-arbeitsplaetzen-suva/filter-detail-suva.htm?WT.mc_id=shortcut_nanopartikel
·
Swiss Nano-Inventory: by the IST, Institute for
Work and Health, supported by the Federal Office of Public Health (BAG), the Federal
Office for the Environment (BAFU), the State Secretariat for Economic Affairs
(SECO), the Swiss National Accident Insurance Fund, and the French Agency for
Occupational and Environmental Health Safety (AFSSET): “Swiss Nano-Inventory –
An assessment of the usage of nanoparticles in Swiss industry” (2008): http://www.suva.ch/ist-nanoinventory.pdf
·
Federal Office of Public Health,” Precautionary
Matrix for Synthetic Nanomaterials”, structured method to assess the "nanospecific
precautionary need" of workers, consumers and the environment, for
enterprises, revised on the basis of users’ experience at the beginning of
2010. http://www.bag.admin.ch/themen/chemikalien/00228/00510/05626/index.html?lang=en ·
Groso A, Petri-Fink A, Magrez A, Riediker M,
Meyer T, (Occupational Safety and Health, School of Basic Sciences, Ecole
Polytechnique Fédérale de Lausanne), “Management of nanomaterials safety in
research environment”, Part Fibre Toxicol. 2010 Dec 10;7:40, http://www.ncbi.nlm.nih.gov/pubmed/21143952 USA: National
Institute for Occupational Safety and Health, NIOSH: ·
Webpages on nanotechnologies and OSH: http://www.cdc.gov/niosh/topics/nanotech/default.html ·
Research on health effect of breathing nanoparticles
(2010):
http://osha.europa.eu/en/news/niosh-research-on-health-effect-of-breathing-nanoparticles ·
Approaches to Safe Nanotechnology - Managing the
Health and Safety Concerns Associated with Engineered Nanomaterials (2009): http://www.cdc.gov/niosh/docs/2009-125/pdfs/2009-125.pdf ·
Research and prevention recommendations
directed at workplace risk assessment:
- Schulte, PA, et al., “Issues
in the development of epidemiologic studies of workers exposed to engineered
nanoparticles” J Occup Environ Med.
2009 Mar;51(3):323-35.. http://www.ncbi.nlm.nih.gov/pubmed/19225418
·
- Trout, DB, Schulte, PA., “Medical
surveillance, exposure registries, and epidemiologic research for workers
exposed to nanomaterials”. Toxicology. 2010 Mar 10;269(2-3):128-35 CANADA ·
Institut de recherche Robert-Sauvé en santé et en
sécurité du travail, IRSST : “Engineered Nanoparticles. Current
Knowledge about OHS Risks and Prevention Measures”. Second Edition, 2010.
http://osha.europa.eu/en/news/CAN-Engineered-Nanoparticles
·
Environment
Canada: Environment Canada issued a notice in
early 2009, requiring companies producing nanomaterials to file federal reports
on those materials describing their toxicity, volume produced, and other
relevant and readily available data. This would be required for all materials
produced in quantities greater than 1 kg. Canada also plans to launch a
voluntary program much like the NMSP in the United States. http://www.ec.gc.ca/subsnouvelles-newsubs/default.asp?lang=En&n=D179F162-1
. Also: “Guide for the Safe Handling of Nanotechnology-based Products” - 2009
Version:
http://www.ec.gc.ca/Publications/default.asp?lang=En&xml=F5DE8BCC-B2B9-4BEB-BB6E-89628B233AE6
AUSTRALIA ·
Safe Work Australia: “Engineered
nanomaterials: Evidence on the effectiveness of workplace controls to prevent
exposure” (2009): http://www.safeworkaustralia.gov.au/ABOUTSAFEWORKAUSTRALIA/WHATWEDO/PUBLICATIONS/Pages/RR200911ENEvidenceOnEffectiveness.aspx
·
Work health and
safety assessment tool for handling engineered nanomaterials – 2010, Safe Work
Australia, http://www.safeworkaustralia.gov.au/AboutSafeWorkAustralia/WhatWeDo/Publications/Pages/AT201008WorkHealthAndSafetyAssessmentTool.aspx 4. Specific EU projects ·
Compendium of Projects in the European
NanoSafety Cluster: The projects appearing in this
compendium are supported financially by the European Union and the Governments
of the FP6 and FP7 Associated States. The Nanosafety cluster will be
coordinated by the Finnish Institute for Occupational Health . 2011 edition:http://www.nanoimpactnet.eu/uploads/file/NanoSafetyCluster/Compendium_2011_web.pdf,
2010 edition ftp://ftp.cordis.europa.eu/pub/nanotechnology/docs/compendium-nanosafety-cluster2010_en.pdf
·
Nanodevice: Novel
Concepts, Methods, and Technologies for the Production of Portable, Easy-to-use
Devices for the Measurement and Analysis of Airborne Engineered Nanoparticles
in Workplace Air http://www.ttl.fi/partner/nanodevice/Pages/default.aspx
·
NANOSH: exposure and
health effects of selected nano-sized particles relevant to the occupational
environment: http://www.ttl.fi/partner/nanosh/Sivut/default.aspx
·
NANOATLAS of selected
engineered nanoparticles. The objective for the Nanoatlas is to present a representative series
of selected nanomaterials including high volume
nanomaterials in commercial applications. NANOATLAS can be
used, e.g., for the detection and measurement of typical engineered nanoparticles in
products, dusts and tissue samples. http://www.ttl.fi/partner/nanosh/progress/Documents/nanosh_nanoatlas.pdf
·
NanoSafe: Safe production
and use of nanomaterials: http://www.nanosafe.org/scripts/home/publigen/content/templates/show.asp?L=EN&P=55&vTicker=alleza
·
NANOGENOTOX:
Safety evaluation of manufactured nanomaterials by characterisation of their
potential genotoxic hazard
http://osha.europa.eu/en/news/eu-nanogenotox ·
Nanocap: acronym for “Nanotechnology Capacity Building NGOs”; Aim: to deepen the
understanding of environmental, occupational health and safety
risks and ethical aspects of
nanotechnology, structure discussion between environmental NGOs, trade unions,
academic researchers and other stakeholders. Health and Safety section: http://www.nanocap.eu/Flex/Site/Page918c.html?SectionID=1785&Lang=UK
After 2009 the individual participants continued their
nano-activities and communicated about this using their own channels (see Contact and partners). 5. International ·
OECD
nanotechnologies Website: http://www.oecd.org/department/0,3355,en_2649_37015404_1_1_1_1_1,00.html,
incl. OECD
Database on Research into the Safety of Manufactured Nanomaterials (http://www.oecd.org/document/26/0,3343,en_2649_37015404_42464730_1_1_1_1,00.html)and Sponsorship
Programme for the Testing of Manufactured Nanomaterials (http://www.oecd.org/document/47/0,3746,en_2649_37015404_41197295_1_1_1_1,00.html)
Three OECD reports address workplace
issues: ·
“Comparison of Guidance on Selection of Skin
Protective Equipment and Respirators for Use in the Workplace: Manufactured
Nanomaterials”. Series on the Safety of Manufactured Nanomaterials Nr 12. ENV/JM/MoONO
(2009)17.: www.oecd.org/dataoecd/15/56/43289781.pdf
·
“Report of an OECD Workshop on Exposure
Assessment and Exposure Mitigation: Manufactured Nanomaterials”. Series on the
Safety of Manufactured Nanomaterials Nr 13, ENV/JM/MONO(2009)18: https://www.oecd.org/dataoecd/15/25/43290538.pdf ·
"Emission Assessment for Identification of
Sources and Release of Airborne Manufactured Nanomaterials in the Workplace:
Compilation of Existing Guidance". Series on the Safety of Manufactured
Nanomaterials Nr 11, ENV/JM/MONO(2009)16, https://www.oecd.org/dataoecd/15/60/43289645.pdf ·
GoodNanoGuide: Collaboration
platform with information on workplace risk assessment and management,
including for specific sectors and types of nanomaterials. Sponsored by, among
others, NIOSH, IRSST, International Council of Nanotechnology: http://goodnanoguide.org/tiki-index.php?page=HomePage
·
Specific ISO standards: ·
ISO/TR 12885:2008 “Health and safety practices
in occupational settings relevant to nanotechnologies” (published) ·
ISO/TR 13329 “Preparation of Material Safety
Data Sheet (MSDS)” (in preparation) ·
ISO/TS 12901-1 “Guidance
on safe handling and disposal of manufactured nanomaterials” (in preparation) ·
ISO/TS 12901-2 “Guidelines
for occupational risk management applied to engineered nanomaterials based on a
"control banding approach" (in preparation) ·
More on the ISO standards on nanotechnologies at
http://www.iso.org/iso/iso_catalogue/catalogue_tc/catalogue_tc_browse.htm?commid=381983 6. Other stakeholders´activities ·
Nordic Council of Ministers: “Evaluation and control of occupational health risks from
nanoparticles”, 2007. Includes an overview of uses and manufacturing of
nanoparticles in the Nordic Countries, a review of methods for exposure and
control measures, occupational exposure scenarios and a review of the quality
of Material Safety Data Sheets. Available at: http://www.norden.org/da/publikationer/publikationer/2007-581/at_download/publicationfile
·
European Trade Union Confederation, ETUC: ·
adopted a second resolution on Nanosciences and
Nanotechnologies http://osha.europa.eu/en/news/eu-etuc-adopted-a-second-resolution-on-nanosciences-and-nanotechnologies ·
contributed to the definition of the term
‘nanomaterials’
http://osha.europa.eu/en/news/eu-etuc-contribution-to-the-definition-of-the-term-2018nanomaterials2019
·
European Federation of Building and Wood
Workers (EFBWW) and European Construction
Industry Federation (FIEC) within the context of the European Social
dialogue: “Nano-products in the
European Construction Industry – State of the art 2009”, http://hesa.etui-rehs.org/uk/newsevents/files/Nano_Executive_%20summary.pdf
Appendix 7
The JRC Nanohub database 1. Background and Scope The JRC NANOhub (http://www.nanohub.eu) is an internationally available database
on nanomaterials with web-based access, hosted by the JRC. It has been developed
on behalf of the JRC as a tool to address nano-safety and measurements of
nanomaterials, supported by an international stakeholder network from academia,
industry, Member States, ISO, CEN, OECD, and NGOs. The JRC NANOhub hosts, among
others, data and studies from the OECD sponsorship programme on the testing of
a representative set of nanomaterials, as well as test and measurement results
on materials from the JRC Repository of Representative Nanomaterials. It serves the needs to: (1)
Host information on nanomaterials in a
structured way (2)
Manage large datasets and collect multiple study
reports for similar nanomaterial endpoints (3)
Minimise time delays for information search and
exchange to further enhance co-operations within research projects The JRC NANOhub database is set up to host
datasets for specific materials (or substances). For each specific material,
information is collected in chapters and sub-chapters (or “endpoints”). The JRC
NANOhub data structure builds on IUCLID chapters and the OECD Harmonised
Templates (OHT). These IUCLID sections have been expanded for nanomaterials-specific
endpoints listed by the OECD WPMN (Working Party for Manufactured Nanomaterials)
in the Guidance Manual of the sponsorship programme. Once the new nanomaterials
sections included in NANOhub have been tested and finalised, they will be
submitted to the OECD for harmonization and implementation in a future release
of IUCLID. Following such a IUCLID update the JRC NANOhub will be able to be
based on IUCLID itself (if needed with using a custom configuration) so that
further developments of IUCLID and IUCLID plug-ins could be used directly. JRC NANOhub provides features to address data
quality, to create reports and dossiers, and to exchange data. It contains
search functions and web-based access functionality and it provides
collaborating parties with a frame for hosting and sharing data. This way it
facilitates cooperation between international parties using the World Wide Web.
The extent to which data are collected in
JRC NANOhub (i.e. the “identification, gathering and upload” of data) now
depends on the use, collection and exchange of data by, user groups, and the
scientific community. The data format of JRC NANOhub does not constitute a
requirement to address all data fields, but it can be seen as comfortable
guidance to which data could contribute to gain an adequate picture of a nanomaterial. 2. Structure The present JRC NANOhub structure provides
the frame for the collection of nanomaterial data. It has three activity
levels: (1)
The collaboration through a project. Each
project and its collaborating parties use their own specific and independent
JRC NANOhub installation, with web-based access. The individual JRC NANOhub
installations are hosted by the JRC. Data exchange between different projects
is an option. (2)
The material(s) investigated within the
collaboration. Data regarding one, several or many specific materials
(substances) are collected and managed in the JRC NANOhub installations as
agreed within a collaboration. (3)
The chapter – subchapter (endpoint / endpoint
study) structure allows entering and modifying data with regard to the
specific material. Users access a project-specific
installation from the www.nanohub.eu
website (Figure 1). Figure 1: Structure of JRC NANOhub: projects hosted
in February 2012 The main chapters of the JRC NANOhub data
structure are shown in Figure 2. 0 || Related Information 1 || General information 2 || Classification and Labelling 3 || Manufacture, use and exposure 4 || Physical and chemical properties 5 || Environmental fate and pathways 6 || Ecotoxicological information 7 || Toxicological information 8 || Analytical methods 9 || Residues in food and feedingstuff 10 || Effectiveness against target organisms 11 || Guidance on safe use 12 || Literature search 13 || Assessment reports Figure 2: Structure of JRC NANOhub: Chapters Within these chapters, the templates for
the properties (or endpoints) were expanded to include, in addition to OHTs,
new templates for nanomaterials taking into account new physicochemical
endpoints, such as aggregation/agglomeration, zeta potential or crystallite
size, as well as in-vitro toxicological information. An example for this format
is shown in Figure 3. Figure 3: Chapter 4: Physicochemical properties and
nanomaterial 3. Features and Functions As a IUCLID derivate, JRC NANOhub is
designed to store, maintain and exchange data coming from research projects.
This comprises features to: (1)
Define materials (substances), endpoint study
records (2)
Enter, update and copy data (including
copy-paste and use of clipboard) (3)
Query and view data (4)
Creation of dossiers for data exchange JRC NANOhub also includes IUCLID features on
reporting and quality control: (1)
Reporting of comprehensive dossiers with
selection options, e.g. regarding confidential information (2)
Creation of dossiers (3)
Quality control including track changes, data
comparison, commenting, reliability scores IUCLID features on administration, user
management and data sharing are also available in JRC NANOhub: (1)
Import, export functions (2)
Filtering and data selection (3)
Share data, dossier submission, compatible with
other programmes (OECD, biocides) (4)
User management and role management 4. Projects hosted today A listing of hosted projects can be found
on www.nanohub.eu. In particular, the OECD WPMN uses the JRC
NANOhub to collect data from its sponsorship programme on safety testing of a
representative set of nanomaterials until a version of IUCLID is available
where a range of nanomaterial specific endpoints has been implemented. 5. Data content Data obtained in the individual projects
are hosted by JRC NANOhub. The data correspond to measurements and studies on
materials from the OECD list of representative nanomaterials, from the European
Repository of Representative Nanomaterials and other materials studied in the
hosted projects. Data quality of individual study entries is
reported in the study dataset. This would comprise e.g. “reliable without
restrictions” for a test study performed under Good Laboratory Practice. Data
quality scores further support the identification of key studies and information,
when large datasets would be merged and several study reports are collected for
similar endpoints. Several consortia have already decided to
share all data; see www.nanohub.eu for an
updated listing. Data today are entered by the individual parties that have
generated the data or identified related information. 6. Data ownership, data access and user
management The JRC provides the database installation
and related service on request. It facilitates the installation and maintenance
of the respective JRC NANOhub installation for a collaborating consortium. The
consortium through its coordinator/representative fully decides about user
access and use of content including sharing of information. User access is for
example managed by the JRC, and fully based on the validation of requests by
the coordinator of a consortium. Contractual agreements regarding the terms
of use within collaboration are dealt with by the consortium. Ownership and
confidentiality of the data or the willingness to share specific data can be declared
and are provided for. One free installation has been installed
under ‘Open Science’, which provides any interested user with an area to
explore the JRC NANOhub tools and features or to provide datasets to any other
user or the scientific community. Access to this specific installation is
granted to all registrants. 7. Further steps JRC envisages to further develop the JRC
NANOhub application, following an upcoming requirements capture exercise with
key stakeholders depending on the available resources and according to an
agreed development plan. In such a development project JRC NANOhub will use as
a basis the future IUCLID version including nanomaterial endpoints and be
embedded in an overall project structure that will encompass not only the full
datasets, but also a viewer (to reduce perceived complexity) and a wrapper
portal providing additional functionality. Appendix 8
Existing product databases on, or with relevance to, consumer products
containing nanomaterials 1. Review of product databases This review is an edited and shortened
version of chapter 3 of the report "Development of
an inventory for consumer products containing nanomaterials" prepared
by RIVM by order and for the account of the Commission.[321] It includes also a short review of a
product database ("nanowerk") not considered in the RIVM report. This annex contains a review on inventories
described in product databases and other databases linked to information on the
use of nanotechnology and nanomaterials. Generally, two types of databases dealing
with nanomaterials/nanotechnology can be distinguished; ‘product databases’ and
‘non-product databases’. Product databases can give answers to questions about
products containing nanomaterials , while questions about specific information
on, for instance, the use of nanotechnology and nanomaterials in general, not
in specific products, may be answered by ‘non-product’ databases. Both types of
databases were studied in this review. 2. Existing
product databases The following items were considered for
each database: –
What is the target group of the database? Who is
going to visit and use the database? –
What is the method of gathering and selecting
products? –
Are criteria defined for the inclusion of
products in the database? –
How are the products categorised? –
What additional information is given on the
database? –
How is the database documented and presented? –
Are there specific countries to which the
database is focused? –
Are there any costs of using the database? These points will be discussed below for
every database provided that the information is available. The following existing product databases
were investigated in the RIVM report: (1)
Woodrow Wilson database (“The Project on
Emerging Nanotechnologies”) (2)
ANEC-BEUC 2010 inventory of consumer products
containing nanomaterials (ANEC-BEUC 2010) (3)
Online database of German Environmental NGO
‘BUND’ (Friends of the Earth Germany) (4)
The Mintel Global New Products Database (GNPD) (5)
Household Products Database Databases 1 to 3 are nano-specific product
databases while 4 and 5 are more general product databases. Concerning the
Household Products Database (5), however, it turned out that the database did
not have a function to find products with a nanoclaim and will not be
considered further here. Below the first four product databases are
described in more detail. 2.1. Woodrow Wilson database The American Woodrow Wilson database was
the first publicly available on-line inventory of nanotechnology-based consumer
products. The inventory claims to be an important resource for consumers,
policymakers, and others who are interested in learning about how
nanotechnology is entering the market. Products have been selected for the Woodrow
Wilson (WW) database by systematic web-based searches. These have ranged from
exploratory searches, through searches on specific categories of goods, to
following leads from multiple sources (including newspapers). According to the database’s website,
products within the database match the following criteria: –
They can be readily purchased by consumers; –
They are identified as ‘nano-based’ (term used
but not explained by Woodrow Wilson) by the manufacturer or by another
source; –
The nano-based claims for the product appear
reasonable. In every case, specific products from
specific producers were identified. Products are categorised in the following
main categories and subcategories (between brackets): –
Appliances (heating,
cooling and air; large kitchen appliances; laundry and clothing care) –
Automotive
(exterior; maintenance and accessories) –
Goods for Children (basics; toys and games) –
Electronics and Computers (audio; cameras and film; computer hardware; display; mobile
devices and communications; television; video) –
Food and Beverage
(cooking; food; storage; supplements) –
Health and Fitness (clothing; cosmetics; filtration; personal care; sporting goods;
sunscreen) –
Home and Garden
(cleaning; construction materials; home furnishings; luxury; paint) –
Cross-Cutting (coatings) However, since nanotechnology has broad
applications in a variety of fields, also a number of ‘generic’ products are
included in the database that are found in many places on the market or
produced by many manufacturers, such as computer processor chips. In addition, one company may offer several
similar nanotechnology-based products and product lines. To avoid redundancy,
for each company just a few samples were included in the WW database. This
means that the database is not describing every product in a product line but
that it provides an initial baseline for understanding how nanotechnology is
being commercialized. The information included for the products
listed in the inventory is the following: information on the manufacturer,
country of origin, product category, claims supporting the application of
nanotechnology, and the date at which the entry was last updated. Hyperlinks to
the manufacturer’s website are also provided. No attempts were made to verify
the nanoclaims of the products. This means that there may be false positives in
the inventory (products of which producers claim that they contain
nanomaterials, but which do not). Furthermore, products that clearly do not use
nanotechnology have been avoided in this database, but some products have
slipped through. For instance, GreenPan cooking utensils were mistakenly
reported to have been manufactured using nanotechnology. This product has been
removed from the database in September 2010. Additions to the inventory have been
made periodically, as new information is received. Since the start of the
project in 2005, the inventory has been updated six times. In the most recent
update of 10 March 2011, 303 new products have been added since the latest
update of August 2009. In the Consumer Products Inventory there are currently
1317 products, produced by 587 companies, located in 30 countries (as of 28
July 2011). For some products, their availability could
no longer be ascertained; to indicate this they were marked ‘Archive’. At the
time these products were added to the inventory ‘live’ links were included.
However, since then the company may have discontinued the product, gone out of
business, removed a self-identifying ‘nano’ claim or simply changed their web
address. In these instances a cached version of the product website was located
using The Internet Archive with a date when the last update has taken place. The database is presented on the website: http://www.nanotechproject.org/inventories/consumer/.
Although the origin of the database is American, it is applicable for global
use. Visiting the website is free of charge. 2.2. ANEC/BEUC 2010 inventory The ANEC/BEUC 2010 inventory is a European
inventory of products, available to consumers, with a claim to contain
nanomaterials. ANEC and BEUC are both European consumers’ organisations
(ANEC: European Association for the Co-ordination of
Consumer Representation in Standardisation, BEUC:
Bureau Européen des Unions de Consommateurs). The target group of the inventory is in principle consumers but the website claims
that ‘it is also useful for citizens, policymakers, and others who are
interested in learning about how nanotechnology is entering the market’. Products
were obtained via internet searches and/or using the feedback of member organisations
of ANEC and BEUC. These member organisations searched products in shops or at
trade fairs, or found them when they tested them in their consumer tests and/or
when they acted in response to requests received from consumers. Products within the ANEC/BEUC database have
to meet two criteria: –
They claim to contain nanomaterials; –
They are available to European consumers. Several product categories are identified
which are of relevance to consumers, which are based on the categories of the
WW database. A detailed table with product categories is provided the following
table. Category || Sub-Category Appliances || Kitchen Appliances Laundry/ Clothing Care Automotive || Maintenance & Accessories Cross Cutting || Coatings Others Electronic & Computers || No subcategory Food & Beverage || Supplements Others Goods for Children || No subcategory Health & Fitness || Clothing Personal Care Sporting Goods Home and Garden || Cleaning Construction Materials Others Additional information on this inventory is
that ANEC/BEUC has been able to check claims in different languages since the
member organisations are located in different European countries. The inventory
has been made twice, in 2009 and in 2010. The update has been carried out in
the same way as the initial inventory. The inventory is a Microsoft Excel table
which is available via the BEUC website: www.beuc.org.
The current inventory contains 475 products. Visiting and using the inventory
is free of charge. 2.3. Online database of German
Environmental NGO ‘BUND’ The product database of BUND (acronym for
Der Bund für Umwelt und Naturschutz Deutschland) is focusing on consumer
products claimed to contain nanomaterials in Germany. The target group of the
website are ‘consumers and everyone else who is interested’. No clear
information is given on the website on how the products are obtained and which
selection criteria were used. The used categorisation for consumer
products is presented in the following table. Category || Subcategory Auto Automotive || Autopflege (car maintenance) Fahrzeugbestandteile (car components) Elektronik und Computer Electronics and Computers || Computer Hardware Electronisches Zubehör und Pflegemittel für Elektronik (equipment and maintenance) Mobiltelefone (mobile phones) Freizeit Leisure || Reiseutensilien, Tassen und Koffer (travelequipment, bags and luggage) Sonstige (other) Sportgeräte und Zubehör (sports equipment and accessories) Gesundheit Health || Sonstige (other) Haus und Garten, Tiere Home,Garden, and (domestic) Animals || Baumaterialien (construction materials) Farben und Lacke (paint) Gärtnern und Landwirtschaft Haustierzubehör und-pflege (pets equipment and maintenance) Möbel (Furniture) Wasch-, Reinigungs- und Pflegemittel (Cleaning and coating products) Haushaltsgeräte Appliances || Große Küchengeräte (Large kitchen appliances) Heizung, Kühlung, Lüftung (Heating, Cooling and Air) Kleingeräte (small appliances) Kochutensilien (cooking utensils) Sonstige (other) Körperpflege Personal Care || Kosmetika (cosmetics) Körperpflegeartikel (personal care products) Lebensmittel und Getränke Foods and Beverage || Kochutensilien (cooking utensils) Lebensmittelaufbewahrung (food package) Nahrungsergänzungsmittel (food supplements) Zuzatzstoffe und Verarbeitungshilfen Medizinische Anwendungen Medical Use || Medizinprodukte (medical products) Produkte für Kinder Goods for Children || Spielzeug (toys) Sonstige Other || Beschichtungen und Pflegemittel für mehrere Anwendungsbreiche (coating for multiple purposes) Textilien und Schuhe Textile and Shoes || Bekleidung und Wäsche (upholstery) Textil- und Schuhpflege (Textile and shoe maintenance/ coating) The BUND database contains about 200
products (March 2011), but it is mentioned that more products will follow shortly.
BUND attempts to give an overview of products that are available in Germany, by
giving a selection of products from different product categories. For further
extension of the list, the cooperation of consumers is requested to bring up
new products. Consumers (in Germany) are called to report all nanomaterial
containing consumer products that are found in shops and that are missing in
the database. The database is accessible on the website of BUND: http://www.bund.net. Using the database is free
of charge. 2.4. Mintel Global New Products
Database (GNPD) The Global New Products Database (GNPD) of
Mintel is a general global product database with manufacturers, agencies and suppliers
as primary target groups. GNPD claims that over 20,000 new products are added
every month, from 49 countries worldwide. Note that GNPD is not nano-specific,
so it is not specifically focused on products with a nanoclaim. GNPD scans the
product labels and stores this information in their database. As a consequence,
products with a nanoclaim can be selected. No specific criteria are mentioned
for products to be included in the database. Nevertheless the database only
includes products that can be purchased in the supermarket. The GNPD is
accessible via the following link: http://www.gnpd.com/sinatra/gnpd/frontpage/&s_item=home. To get information from the GNPD a paid license is required. A product database not considered in the
report by RIVM is The Nanotechnology Products database of "nanowerk" Nanowerk.com
is a nanotechnology and nanosciences portal developed and maintained by US-based
Nanowerk LLC. Its Nanotechnology Products database provides an overview of how nanomaterials
and nanostructuring applications are used today in industrial and commercial
appplications across industries. The database is presented on the website: http://www.nanowerk.com/products/products.php The origin of the database is American, but it is applicable for
global use. The criteria for inclusion of products are not explicitly defined.
Information is collected via web searches and by input from product
manufacturers and consumers. It uses the categorisation: –
Chemicals –
Commodities –
Construction –
Energy –
Environment –
Food –
Industrial –
Information and Communications Technology –
Medical –
Precision Engineering –
Textiles and Garments –
Transportation The Nanotechnology Products database of nanowerk
contains 177 products (July 2011), with information on the products provided by
the product manufacturer, and includes links to the manufacturer's product web
page. The database is public and visiting it is
free of charge. 3. The REACH registration database REACH[322] is
the European Union Regulation on chemicals and their safe use. It deals with the
Registration, Evaluation, Authorisation and Restriction of Chemical substances.
The Regulation entered into force on 1 June 2007. The REACH Regulation places greater
responsibility on industry to manage the risks from chemicals and to provide
safety information on the substances. Manufacturers and importers are required
to gather information on the properties of their chemical substances, which
will allow their safe handling, and to register the information in a central
database run by the European Chemicals Agency (ECHA) in Helsinki. The Agency
acts as the central point in the REACH system and manages the REACH-IT database. REACH is specific for substances and it is
possible to indicate that the registered substance is a nanomaterial or
includes nanoforms in REACH registrations (for example, there is a voluntary
tick-box to identify the substance or form of a substance as a nanomaterial).
This information is retrievable from the registration database.[323] It is however not always easy to identify which information relates
to the nanoform(s) and which information to the bulk form(s) of the substances.
Also, the description of uses in REACH dossiers is rather generic, and
therefore it is not possible to identify concrete applications from the REACH
dossiers. A screening of the REACH registration dossiers and CLP notifications
was performed to identify information about substances in the nanoform.
Methodology and outcome of this work is reported in Appendix 3. 4. Other
databases linked to the use of nanotechnology In addition to the product databases
discussed above, below an overview is presented on databases not predominantly
considering products, but containing information related to the potential
toxicity or hazard of nanomaterials. Two of the databases mentioned in the
current section provide information on experimental data and the projects
and/or organisations in which these data are obtained. Two other databases
specifically focus on industry needs. (1)
The OECD Database on Research into Safety of Manufactured Nanomaterials (2)
JRC NanoHub (3)
nanotech-data.com (4)
nanoproducts.de 4.1. The OECD Database on
Research into Safety of Manufactured Nanomaterials The OECD Database on Research into Safety
of Manufactured Nanomaterials is a publicly available database of the Organisation for Economic Co-operation and Development
(OECD). It is an inventory of safety research information on manufactured
(engineered) nanomaterials. The database contains information relevant to
research on the environmental, health, and safety aspects of nanomaterials. The
information is and will be based on projects that are planned, underway or
completed. The details on the data on nanomaterials gathered in these projects
may not be available via this database before they are published in the
scientific literature. The OECD database has been developed as
part of the OECD activities to promote international co-operation in addressing
human health and environmental safety aspects of manufactured nanomaterials. It
is also intended to be an inventory of information on research programmes to
help other projects of the OECD Working Party on Manufactured Nanomaterials
(WPMN). This help may consist of identifying relevant research projects or
storing information derived from the projects of the WPMN (including the
sponsorship programme on the testing of manufactured nanomaterials). The following information is stored in
distinct fields: –
Project Title; Start date; End date; –
Project Status (Current; planned; or completed);
–
Country or organisation; –
Funding information (where available, on
approximate total funding; approximate annual funding; and funding source); –
Project Summary; Project URL; Related web links;
–
Investigator information: name, research
affiliation, contact details; –
Categorisation by material name, relevance to
the safety, research themes, test methods; –
Overall outcomes and outputs of the project. The site is publicly and freely available
via: (http://webnet.oecd.org/NanoMaterials/Pagelet/Front/Default.aspx) 4.2. JRC NANOhub[324] The JRC NANOhub is a comprehensive IT
platform (http://www.nanohub.eu), dedicated to the management of safety/risk assessment information
of nanomaterials (substances). The information
gathered in this database is obtained from different EU projects as well as various OECD WPMN activities (Sponsorship programme for testing of a set of representative
nanomaterials). The database consists of
physicochemical properties and toxicity data of various engineered nanomaterials. These data are not publicly available. 4.3. Nanotech-data.com Nanotech-data.com is the Database of
Nanotechnologies for Luxembourg and areas in Germany and Belgium (Luxembourg,
Lorraine, Rhineland-Palatinate, Saarland, Wallonia). The aim of the database is
to inform about existing
products, patents, processes, demands, news and events in the field of
nanotechnology and to stimulate the knowledge transfer between research, Small
to Medium-sized Enterprises (SME’s) and large companies. The target public of
this website are SME’s, firms, researchers, institutions and individuals. The
website provides detailed information about existing products, methods and
services, application of interactive internet tools, simple and efficient
handling and it is free of charge. The site is publicly and freely available
via http://www.nanodaten.de/site/page_de_garde.html. 4.4. Nanoproducts.de The website nanoproducts.de is a freely
accessible internet database that deals with the marketing of products
containing nanomaterials and/or products produced with nanotechnology on the
internet. According to the website ‘it offers services to industry in the area
of product and technology transfer’. In this database, more than 450 different
nanotechnology products are presented. The product spectrum comprises the
fields of process engineering, analytics, raw materials, materials and
commercial products. The aim is to list all commercial and non-commercial
nanotech products and technologies. The website http://nanoproducts.de/ is publicly available; using it is free of charge. Appendix 9
Standardisation Standardisation is a process of consensus
building on topics of technical-commercial nature, but also on items of broader
societal relevance, in order to improve and facilitate communication, trade,
innovation and transfer of technology. One distinguishes 'documentary' or
'written' standards (see section 1.) from physical or material standards (see
section 2.). Both written and physical standards play an important role in
harmonising multiple aspects of society and our daily lives, increasingly also
those aspects that are related to nanotechnology. 1. Documentary standard development
activities 1.1. General overview of actors
and activities in nanotechnology standardisation The International Organization for
Standardization (ISO) is the larger of the non-governmental standard
development organisations (SDOs) and provides a global forum for the
development of 'documentary' or 'written' standards (as opposed to physical or
material standards; see 2.). In the field of nanotechnologies, the ISO
Technical Committee 'Nanotechnologies' (ISO/TC 229) plays a central role. It
was created to complement and coordinate the nano-relevant standardisation work
already undertaken by other, older ISO TCs. Similar responsibilities are
carried by IEC/TC 113 and CEN/TC 352 in their respective mother SDOs (IEC, the
International Electrotechnical Commission, and CEN, the European Committee for
Standardization). Another major player in the nanotechnology standardisation
area is the Organisation for Economic Cooperation and Development (OECD), which
has devoted two working parties to the topic (Working Party on Manufactured
Nanomaterials, WPMN, and Working Party on Nanotechnology, WPN). There are also
a number of international organisations involved in the measurement aspects of
standardisation, such as CIPM, the international metrology organisation, or
VAMAS (the Versailles project on Advanced Materials and Standards), active in
pre-normative research. To facilitate the coordination of the work
of the different SDOs the Nanotechnologies Liaison Coordination Group (NLCG)
was created in 2008. The NLCG is hosted by ISO/TC 229. Twice a year,
representatives of the NLCG members[325]
discuss issues of common interest, in order to improve harmonisation (for
example of terminology) and to avoid unnecessary duplication in a time where
resources are limited and in an area where expectations from regulators and
from the public are high. The agenda of the NLCG meetings is organised based on
the periodic liaison reports submitted by the members.[326] Over the last three years, since the
publication of the previous EC Regulatory Review, a number of specific
nanotechnology standards and reports have been released, especially, but not
only, by ISO/TC 229.[327],[328],[329],[330],[331],[332],[333],[334],[335],[336],[337],[338],[339],[340],[341],[342],[343],[344],[345],[346],[347],[348],[349] Currently, the
CEN/TC 352 activities are dominated by the European Commission
standardisation mandate M461, which requires the development of standards on about
40 different nanotechnology subjects. Since most of these 40 topics correspond
to a number of documents, the size of this M461 mandate is unprecedented. For
each of these items at least one standardisation committee has already
indicated its intention to contribute to the development of the required
documents. This currently concerns 7 ISO TCs, 6 CEN TCs and 1 IEC TC. While a
number of the listed items in the mandate are already under development, work
on the majority of items has yet to start. For some items this will require
substantial pre-normative research, with an as large as possible international
collaboration, for example through organisations such as VAMAS, or through EU-funded
research (via CEN and the standardisation mandate, or directly via the Research
funding programmes). Coordination of the M461 work will be carried out by
CEN/TC 352. CEN/TC 352 and ISO/TC 229 co-operate through the Vienna agreement. This
agreement is an important tool for European standardisation efforts in the nanotechnology
area because the jointly developed EN ISO standards reconcile the desire of the
EU legislator to refer to EU-wide adopted standards, with the preference of
major EU Member States to develop the standards at the most international
standardisation level possible (i.e. at ISO level). Until February 2012, CEN/TC
352 has only released 4 documents, each co-developed with ISO/TC 229, under the
Vienna Agreement, with ISO lead. 1.2. Standard terminology and
nomenclature ISO and IEC have a joint working group
(JWG1) for work on terminology and nomenclature. CEN has explicitly chosen to
not develop a nanotechnology terminology of its own, but to use its liaison
status and the Vienna Agreement to co-develop the ISO terminology. A detailed
analysis of the ISO/IEC/CEN terminology related to nanomaterials is given in
Appendix 1. The core elements of a series of terminology documents (EN ISO/IEC
80004-x) have been released over the last three years. Document 1 in this
series (ISO/IEC TS 80004-1, released in 2009)[350] defines terms such as
nanotechnology, nanoscience, nanoscale and nanomaterial.[351] The first terminology
document published by ISO/TC 229, the EN ISO TS 27687 document,[352] with the definition of the
terms nano-object and nanoparticle, is currently under revision and will be
released after revision as the ISO TS 80004-2 document. ISO TS
80004-3 covers the carbon nanomaterials (such as carbon nanotubes)[353] and ISO TS 80004-4 deals with
nanostructured materials.[354]
ISO TS 80004-5 is a document defining terms for use in the field of
nanobiotechnology,[355]
and a number of similar terminology documents, specific for a certain field of
nanotechnology (manufacturing, medicine, etc.) are under development.
Conveniently, the complete list of terms and definitions in these documents,
and in all other ISO documents, can be consulted in the ISO Concepts Database (http://cdb.iso.org). Complementary to the work on terminology is
the work on nomenclature. ISO and IUPAC, the International Union for Pure and
Applied Chemistry, have recently decided to join their forces on this subject,
and to develop a nomenclature for nano-objects in IUPAC, with help of ISO/TC
229. 1.3. Standard measurement
methods Several technical committees (TCs), in
particular ISO TC 24/SC 4 (Particle characterisation),
ISO/TC 201 (Surface chemical analysis) and ISO/TC 202 (Microbeam
analysis), have already in the past developed standardised methods for
measurements at what is now called the nanoscale. Naturally, this work continues
in these committees. ISO/TC 229 and IEC/TC 113 complement (but not replace)
the work of other technical committees on measurement methods not yet covered
by other technical committees, for example on the characterisation of carbon
nanotubes [356],[357],[358],[359],[360],[361],[362],[363],[364] or on the creation of
reproducible nanoparticle aerosols for inhalation toxicity testing.[365],[366] The specific CEN output in this area is
likely to increase due to the standardisation mandate M461. This mandate, given
by the European Commission to the European SDOs (CEN, CENELEC and ETSI) is
focused on the areas of measurement and testing tools for the characterisation
of nanomaterials and their behaviour, and to assess exposure to nanomaterials,
complementing work carried out in the framework of OECD-WPMN and in the context
of the implementation of REACH and CLP Regulations. Examples of mandated items
for standardisation are methods for the detection, identification and
quantification of the nanomaterial content of 'matrix materials', which can be
consumer products (food, cosmetics, etc.), but also environmental materials
(soils, water, sludge, etc.). The development of a comprehensive set of
reliable methods for the detection of minute amounts of nanomaterials in such
matrices will require years of research. This work has started already in
projects supported by previous and current EU Framework Programmes for Research
(for example FP7 project NanoLyse). A particular set of measurement-related
deliverables of the OECD are the OECD Test Guidelines, which are used to
underpin the OECD Mutual Acceptance of Data (MAD) policy. MAD has been
developed to relieve some of the burden of testing and assessing chemicals, and
requires laboratories to implement Good Laboratory Practice (GLP). A similar
concept is used by the world metrology organisation (CIPM) which has developed
the International System of Units (SI) and tools (such as the Mutual
Recognition Arrangement, MRA) to make measurement results SI-traceable, and
therefore globally comparable. The culture of measurement laboratory
accreditation, in accordance with, for example, ISO/IEC 17025,[367] is slowly spreading into the
nano-analysis area. 1.4. Conclusions An important part of the efforts of SDOs
such as ISO, CEN, IEC and OECD, in the nanotechnology area, is aimed at
describing and specifying nanomaterials. These efforts should allow to
distinguish and categorise different types of nanomaterials, based on new
nanomaterial-specific terminology and nomenclature, and to develop measurement
methods that allow one to verify the properties that are characteristic for one
nanomaterial category or another. This approach should further enable moving
from the 'case-by-case' approach in the assessment and evaluation of
nanomaterials, which is limited, laborious and slow dealing with a limited
number of materials, to a category approach, where data obtained on one
material can be rightfully judged to be relevant for another more or less
similar material. 2. Reference materials and representative
test materials In the field of measurement and testing,
the aspect of quality assurance is valued more and more. Essential tools in the
development and validation of reliable test methods and in the establishment of
quality control of routine measurement processes are reference materials and
representative test materials. 2.1. Reference materials Reference materials are materials which are
carefully analysed for one or more of their properties, and which carry the
obtained information (typically assigned property values) in a way that it can
be used in measurement processes. Performing measurements on CRMs, and
comparing the measured values with the attributed traceable certified property
values, is not the only way for a laboratory to prove its proficiency, but it
is certainly the most time-effective method, provided the appropriate CRM is
available. The possibility to provide such proof of proficiency is essential
for laboratories that are required to produce measurement results that will be
compared against, for example, regulatory limits. In the last three years, the European
Commission, via its Joint Research Centre, has contributed significantly to the
development of an increasing number of non-certified nanoscale reference
materials, which are needed for method development, control charts and
interlaboratory studies. A particular success was the release of a first
colloidal silica certified reference material (CRM). CRMs have certified
property values, which are needed for method validation and proficiency
testing. The ERM-FD100 colloidal silica has certified property
values for several equivalent diameters of the constituent silica
particles.[368]
Current reference material development is working on more complex
nanoparticulate systems (bimodal, polydisperse), in line with the measurement
needs imposed by the new EU nanomaterial definition. Another main RM producer
active in the nano-field is NIST (USA), which has released reference materials
consisting of Au-nanoparticles and of carbon nanotubes. 2.2. Representative test
materials The characterisation of a particular
property for a reference material requires the availability of a validated test
method to assess that property. In the field of nanotechnology, there are a
large number of newly developed test methods that are still to be validated.
Also the applicability of existing, validated test methods to nanomaterials is
sometimes questioned. In this case, that is, in the absence of validated test
methods, reliable property values cannot be assigned, and therefore reference
materials cannot be produced. Nevertheless, the level of consensus about the
applicability of certain test methods can be increased by carrying out
experiments in different laboratories on a common set of test materials. In the
OECD-WPMN sponsorship programme a number of materials has been selected based
on their representativity for the commercially available (or expected to be
available) nanomaterials. These materials are used in the international
interlaboratory evaluation of existing OECD test guidelines, the so-called
Sponsorship Programme (see section 5.4). The European Commission, via its JRC,
has contributed to this programme by the development of a series (NM-xxx) of
such nanomaterials. They are primarily intended for the participants in the
OECD-WPMN sponsorship programme, but samples can also be obtained by other
researchers (http://ihcp.jrc.ec.europa.eu/our_activities/nanotechnology/nanomaterials-repository). [1] http://www.europarl.europa.eu/sides/getDoc.do?type=TA&reference=P6-TA-2009-0328&language=EN [2] Follow-up to the European Parliament resolution on
regulatory aspects of nanomaterials, adopted by the Commission on 14 July 2009. [3] Regulation (EC) No 1907/2006 of the European
Parliament and of the Council of 18 December 2006 concerning the Registration,
Evaluation, Authorisation and Restriction of Chemicals (REACH), OJ L 396,
30.12.2006, p. 1. [4] Regulation (EC) No 1272/2008 on classification,
labelling and packaging (CLP) of substances and mixtures, OL L 353, 31,12,2008,
p.1. [5] http://www.consilium.europa.eu/uedocs/cms_data/docs/pressdata/en/envir/118646.pdf [6] OJ L 275, 20.10.2011, p.38. [7] i.e. forms of titanium dioxide with more than 50% of
particles in the size range 1-100 nm. [8] For discussion of the terminology used, see http://ec.europa.eu/enterprise/sectors/chemicals/files/reach/nanomaterials_en.pdf. [9] OJ L 275 20.10.2011 p 38, http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=OJ:L:2011:275:0038:0040:EN:PDF. [10] Resolution European Parliament on Regulatory Aspects of
Nanomaterials (2008/2208(INI)
24.4.2009. [11] https://cdb.iso.org/cdb/termentry!display.action?entry=497556&language=1 [12] http://ec.europa.eu/dgs/jrc/index.cfm?id=2540 [13] http://ec.europa.eu/health/scientific_committees/emerging/docs/scenihr_o_032.pdf [14] http://ec.europa.eu/environment/consultations/nanomaterials.htm [15] G. Lövestam et al., JRC Reference Report, EUR 24403 EN,
ISBN 978-92-79-16014-1, Luxembourg: Publications Office of the European Union,
2010; http://ec.europa.eu/dgs/jrc/index.cfm?id=2540. [16] http://ec.europa.eu/health/scientific_committees/emerging/docs/scenihr_o_032.pdf [17] J. Ramsden, The nanoscale, Nanotechnology
Perceptions, Vol. 5, p. 3-25 (2008). [18] Validation of
dynamic light scattering and centrifugal liquid sedimentation methods for
nanoparticle characterisation, A. Braun, O. Couteau, K. Franks, V. Kestens, G.
Roebben, A. Lamberty, T.P.J. Linsinger, Advanced Powder Technology, Vol.
22, p. 766-770 (2010). [19] Measurement of the
size of spherical nanoparticles by means of atomic force microscopy, O.
Couteau, G. Roebben, Measurement Science and Technology, Vol. 22, 065101
(2011). [20] Interlaboratory
comparison for the measurement of particle size and zeta potential of silica
nanoparticles in an aqueous suspension, A. Lamberty, K. Franks, G. Roebben, A.
Braun, V. Kestens, T. Linsinger,. Journal of Nanoparticle Research,
Vol.13, p. 7317-7329 (2011). [21] Interlaboratory
Comparison of Size and Surface Charge Measurements on Nanoparticles prior to
Biological Impact Assessment, G. Roebben, S. Ramirez-Garcia, V. Hackley, M. Roesslein,
F. Klaessig, V. Kestens, I. Lynch, M. C. Garner, A. Rawle, A. Elder, V. Colvin,
W. Kreyling, H. Krug, Z. Lewicka, S. McNeil, A. Nel, A. Patri, P. Wick, M. Wiesner,
Tian Xia, G. Oberdörster, K. Dawson, J. Nanoparticle Research, Vol. 13,
p. 2675-2687, (DOI) 10.1007/s11051-011-0423-y (2011). [22] Reference materials
for measuring the size of nanoparticles, T. P. J. Linsinger, G. Roebben, C.
Solans, R. Ramsch, Trends in Analytical Chemistry, Vol. 30, p. 18-27
(2011). [23] Certification of equivalent spherical diameters of
silica nanoparticles in water, ERM-FD100, A. Braun, K. Franks, V. Kestens, G.
Roebben, A. Lamberty, T. Linsinger, Report EUR 24620 EN, European Union,
Luxembourg, ISBN 978-92-79-18676-9, 2011. [24] Nanoscale reference materials, G. Roebben, G. Reiners,
H. Emons, in Nanotechnology Standards, Eds V. Murashov, J. Howard, Springer
Science+Business Media, New York, NY, ISBN – 978-1-4419-7852-3 (2011). [25] Separation
and characterization of gold nanoparticle mixtures by flow-field-flow
fractionation, L. Calzolai, D. Gilliland, C. P. Garcia, F. Rossi, J.
Chromatography A, Vol. 1218, p. 4234 – 4239 (2011). [26] Roco, M. C. 2004. Nanoscale Science and Engineering:
Unifying and Transforming Tools. AIChE Journal, 50(5): 890-897. [27] Roco, M. C. 2007. National Nanotechnology Initiative–
Past, Present, Future.” In Goddard, W. A., et al. eds. Handbook on
Nanoscience, Engineering and Technology, Boca Raton, FL, CRC Press; pp.
3.1-3.26. [28] http://www.epa.gov/osa/pdfs/nanotech/epa-nanotechnology-whitepaper-0207.pdf,
p. 12. [29] Stefan Schlag, Bala Suresh, Masahiro Yoneyama and
Vivien Yang, http://www.sriconsulting.com/SCUP/Public/Reports/NANOT000/;
except for carbon black: Chemical Economic Handbook report on carbon black http://www.sriconsulting.com/CEH/Public/Reports/731.3000/;
Source: IHS Inc. The use of this content was
authorized in advance by IHS. Any further use or redistribution of this
content is strictly prohibited a without written permission by IHS. All rights
reserved. [30] The Commission has also received estimates which are
higher than this but still in the same rough order of magnitude. [31] chemical mechanical planarisation [32] Some of the described uses, e.g. semiconductor chips
may relate to nanostructured materials rather than nanomaterials in the sense
of the nanomaterial definition. [33] http://ec.europa.eu/enterprise/sectors/ict/key_technologies/kets_high_level_group_en.htm [34] For a list of effects and property improvements through
nanotechnologies see appendix 4. [35] According to Ireland’s Nanotechnology Commercialisation
Framework 2010 – 2014, Forfas, (Aug.2010)
http://www.forfas.ie/media/forfas310810-nanotech_commercialisation_framework_2010-2014.pdf. http://ec.europa.eu/enterprise/sectors/ict/key_technologies/kets_high_level_group_en.htm;
and according to OECD, "Nanotechnology: an overview based on indicators
and statistics" (2009), based on Roco, MC and WS Bainbridge, Societal
Implications of Nanoscience and Nanotechnology, Kluwer Academic Publ, (2001);
both quoted from http://ec.europa.eu/enterprise/sectors/ict/files/kets/hlg_report_final_en.pdf,
p.13. [36] http://ec.europa.eu/enterprise/sectors/ict/files/kets/hlg_report_final_en.pdf,
p. 13. [37] Source: Cross-sectoral Analysis of the Impact of
International Industrial Policy on Key Enabling Technologies (Danish
Technological Institute with IDEA Consult, 2011), Institute of Nanotechnology,
(analysis from UNU-MERIT and VDI-TZ), 2010, OECD (2009): Nanotechnology: An
Overview based on Indicators and Statistics:
http://www.oecd.org/dataoecd/59/9/43179651.pdf,
http://www.fas.org/sgp/crs/misc/RL34511.pdf. [38] This figure seems in contradiction to the findings of
appendix 2. A possible explanation is that the authors of the work at the basis
of the KET reports may have focused on new, technologically innovative
applications whereas appendix 2 indicates that by far the highest share of
nanomaterial applications is in long established commodity applications, on
which the different world regions are likely to have market shares similar to
their share in overall economic activities. [39] http://www.gaia.fi/files/680/Study_on_REACH_contribution_to_emerging_technologies_Situation_in_Nanotech_companies_in_Europe_DRAFT.pdf [40] Brazil, Russia, China, India [41] According to Directive 98/24/EC, the term ‘hazard’ means the intrinsic property of a chemical agent with the
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products containing nanomaterials", http://ec.europa.eu/environment/chemicals/nanotech/pdf/study_inventory.pdf. [175] http://apps.echa.europa.eu/registered/registered-sub.aspx#phasein [176] http://www.observatorynano.eu/project/ [177] http://www.nanotechproject.org/inventories/consumer/ [178] www.beuc.org [179] http://www.bund.net [180] http://www.nanowerk.com/products/products.php [181] for more information: http://nanomaterialsconf.eu/documents/Nanos-Reporting-Mechanisms.pdf. [182] http://ec.europa.eu/environment/chemicals/nanotech/index.htm [183] The ISO definitions of these terms can be found in the
ISO Concepts database (http://cdb.iso.org). [184] The fact that the EU definition does not refer to
“approximately” 1-100 nm will in practice play little role in this typology
which is not intended to refer to individual borderline cases but rather to
general patterns. [185] ISO TS 80004-1:2010 Nanotechnologies – Vocabulary – Part
1: Core terms [186] CEN ISO TS 27687:2009 Nanotechnologies – Terminology and
definitions for nanoparticles [187] ISO TS 80004-1:2010 Nanotechnologies – Vocabulary – Part
1: Core terms [188] ISO TS 80004-1:2010 Nanotechnologies – Vocabulary – Part
1: Core terms. [189] ISO Technical specifications shall be reviewed at least
every three years to decide either to confirm the technical specification for a
further three years, revise the technical specification, process it further to
become an International Standard or withdraw the technical specification. After
six years, a technical specification shall be either converted into an
International Standard or withdrawn. [190] ISO TS 80004-4:2011 Nanotechnologies – Vocabulary – Part
4: Nanostructured Materials. [191] ISO 3252:1999 Powder metallurgy – Vocabulary. [192] ISO 1942-2-:1989, Dental vocabulary – Part 2: Dental
materials. [193] R.J. Hunter, Foundations of Colloid Science, Oxford
University Press, 2001. [194] http://ec.europa.eu/environment/chemicals/nanotech/questions_answers.htm,
question 3. [195] http://ec.europa.eu/environment/chemicals/nanotech/questions_answers.htm,
question 3. [196] Source: IHS Inc. The use of
this content was authorized in advance by IHS. Any further use or
redistribution of this content is strictly prohibited a without written
permission by IHS. All rights reserved. Reports used:
Stefan Schlag, Bala Suresh, Masahiro Yoneyama
and Vivien Yang, http://www.sriconsulting.com/SCUP/Public/Reports/NANOT000/;
references to SRI in this annex refer to this report, except for carbon black,
where information was taken from the Chemical Economic Handbook report on
carbon black http://www.sriconsulting.com/CEH/Public/Reports/731.3000/.
[197] http://www.observatorynano.eu/project/catalogue/2CH/ [198] http://www.nanopartikel.info/cms/lang/en/Projekte/dana;
note that the database in many cases refers to “high dose” experiments. Such
“high dose”-experiments describe situations which do usually not occur in
normal life, neither for a customer nor at an industry’s workplace. High dose
exposures could occur in case of an accident or a wanted uptake of nanoobjects. [199] http://apps.echa.europa.eu/registered/registered-sub.aspx#phasein [200] Document CASG Nano/03/2011. [201] Engineered Nanoparticles - Review of Health and Environmental
Safety (ENRHES), http://ihcp.jrc.ec.europa.eu/whats-new/enhres-final-report. [202] http://www.nanopartikel.info/cms/lang/en/Wissensbasis [203] In terminology developed in the framework of REACH
implementation “substances at the nanoscale”; for discussion of this
terminology, see http://ec.europa.eu/enterprise/sectors/chemicals/files/reach/nanomaterials_en.pdf.
Normally, substances are described in their chemical identity, as defined in
REACH. [204] For an explanation of the term “reaction mass”, see
REACH guidance on substance identification and naming http://guidance.echa.europa.eu/docs/guidance_document/substance_id_en.pdf, p. 21. [205] Roco, M. C. 2004. Nanoscale Science and Engineering:
Unifying and Transforming Tools. AIChE Journal, 50(5): 890-897. [206] Roco, M. C. 2007. National Nanotechnology Initiative–
Past, Present, Future.” In Goddard, W. A., et al. eds. Handbook on
Nanoscience, Engineering and Technology, Boca Raton, FL, CRC Press; pp.
3.1-3.26. [207] http://www.epa.gov/osa/pdfs/nanotech/epa-nanotechnology-whitepaper-0207.pdf,
p. 12. [208] The term “comparable” is to be understood as leaving a
degree of uncertainty on the exact levels, thus it could not be excluded that
Europe is slightly weaker in relative terms of nanomaterial uptake than e.g.
the US or Japan. [209] This can be different depending on process details. [210] CEFIC, contribution received as part of the consultation
on a draft version. [211] To be distinguished from "silica fume" which
is a by-product from thermal silicon production processes, CEFIC, contribution
received as part of the consultation on a draft version. [212] Synonymous for synthetic amorphous silica; public
information available on:
http://apps.echa.europa.eu/registered/data/dossiers/DISS-76fd35e0-69c4-29a3-e044-00144f26965e/DISS-76fd35e0-69c4-29a3-e044-00144f26965e_DISS-76fd35e0-69c4-29a3-e044-00144f26965e.html. [213] Except for respiratory sensitisation and hazardous to
the ozone layer (data lacking), all fields for health and environmental hazards
indicate that the registrant considers data for those hazards as conclusive but
not sufficient for classification. [214] EU-OSHA, Workplace exposure to nanoparticles,
Luxembourg, 2009. Available at:
http://osha.europa.eu/en/publications/literature_reviews/workplace_exposure_to_nanoparticles/view [215] For an overview of relevant literature see: http://nanopartikel.info/cms/lang/en/Wissensbasis/siliciumdioxid/template/element2Category2ContainerList?catTitle=Exposure&containerID=384&queryPath=/content/jahia/dana/ContentPage_3/Wissensbasis/siliciumdioxid/element2Category2ContainerList/ContentContainer_384;
see also: Presence and risks of nanosilica in food products, Dekkers, S.;
Krystek, P.; Peters, R.B.J.; Lankveld, D.P.K:; Bokkers, B.G.H.; van
Hoeven-Arentzen, P.H.; Bouwmeester, H. and Oomen A.G.; Nanotoxicology, 2010,
Barly Online, 1-13, and comments in a letter to the editor in: Nanotoxicology, 2011; Early
Online, 1–3. [216] http://www.ecetoc.org/index.php?mact=MCSoap,cntnt01,details,0&cntnt01by_category=3&cntnt01order_by=Reference%20Desc&cntnt01template=display_list_v2&cntnt01display_template=display_details_v2&cntnt01document_id=122&cntnt01returnid=91 [217] http://www.efsa.europa.eu/en/efsajournal/doc/1132.pdf [218] European schedule of occupational diseases (notified
under document number C(2003) 3297). [219] As part of the rubber matrix. [220] Information from contributions to the CASG(Nano)
consultation and joint work between ECHA and the Commission services analysing
a number of registration dossiers in more detail. [221] For an explanation of the use of the term “bulk”, see
Nanomaterials in REACH, p.5, http://ec.europa.eu/enterprise/sectors/chemicals/files/reach/nanomaterials_en.pdf. [222] Public
information available on:
http://apps.echa.europa.eu/registered/data/dossiers/DISS-9eaff323-014a-482f-e044-00144f67d031/DISS-9eaff323-014a-482f-e044-00144f67d031_DISS-9eaff323-014a-482f-e044-00144f67d031.html. [223] Except for hazardous to the ozone layer (data lacking),
all fields indicate that the registrant considers data for all endpoints as conclusive
but not sufficient for classification. [224] Engineered Nanoparticles - Review of Health and
Environmental Safety (ENRHES), http://ihcp.jrc.ec.europa.eu/whats-new/enhres-final-report,
p. 141. [225] http://www.cdc.gov/niosh/docs/2011-160/pdfs/2011-160.pdf [226] Titanium Dioxide Nanoparticles Induce DNA Damage and
Genetic Instability In vivo in Mice, Trouiller, B.,
Reliene, R., Westbrook, A., Solaimani, P., Schiestl, R.H., Cancer Res November
15, 2009 69; 8784. Available at
http://cancerres.aacrjournals.org/content/69/22/8784.full. [227] Titanium dioxide has been in
2006 classified by the International Agency for Research on Cancer (IARC) as an
IARC Group 2B carcinogen ''possibly carcinogen to humans; http://monographs.iarc.fr/ENG/Monographs/PDFs/93-titaniumdioxide.pdf. [228] Occupational Exposure to Titanium Dioxide, Current
Intelligence Bulletin 63: Occupational Exposure to Titanium Dioxide, National
Institute for Occupational Safety and Health 2011. Available at
http://www.cdc.gov/niosh/docs/2011-160/; further literature see also:
http://nanopartikel.info/cms/lang/en/Wissensbasis/Titandioxid/template/element2Category2ContainerList?catTitle=Exposure&containerID=46&queryPath=/content/jahia/dana/ContentPage_3/Wissensbasis/Titandioxid/element2Category2ContainerList/ContentContainer_46. [229] For further information see : http://nanopartikel.info/cms/lang/en/Wissensbasis/Titandioxid/template/element2Category2ContainerList?catTitle=Exposure&containerID=46&queryPath=/content/jahia/dana/ContentPage_3/Wissensbasis/Titandioxid/element2Category2ContainerList/ContentContainer_46,
section on environmental exposure. [230] Public
information available on: http://apps.echa.europa.eu/registered/data/dossiers/DISS-9eb185b3-df52-333c-e044-00144f67d031/AGGR-fbd39734-7544-4e5a-8f87-2e1d877da115_DISS-9eb185b3-df52-333c-e044-00144f67d031.html. [231] Except for the classification as Aquatic Chronic 1H410: Very toxic to aquatic life with long lasting
effects, and for hazardous to the aquatic environment
(acute/short-term) (data lacking), all other fields indicate that the
registrant considers data for all other endpoints as conclusive but not
sufficient for classification. [232] Zinc oxide, Registry of Toxic Effects of Chemical
Substances RTECS #: ZH4810000, http://www.cdc.gov/niosh-rtecs/ZH496510.html#P;
NIOSH Pocket Guide to Chemical Hazards,
http://www.cdc.gov/niosh/npg/npgd0675.html. [233] http://nanopartikel.info/cms/lang/en/Wissensbasis/Zinkoxid/template/element2Category2ContainerList?catTitle=Exposure&containerID=528&queryPath=/content/jahia/dana/ContentPage_3/Wissensbasis/Zinkoxid/element2Category2ContainerList/ContentContainer_528 [234] Observatory Nano – http://www.observatorynano.eu/project/document/79/. [235] As part of the rubber matrix. [236] Public
information available on: http://apps.echa.europa.eu/registered/data/dossiers/DISS-9eb4460f-9f3a-575c-e044-00144f67d031/DISS-9eb4460f-9f3a-575c-e044-00144f67d031_DISS-9eb4460f-9f3a-575c-e044-00144f67d031.html;
http://apps.echa.europa.eu/registered/data/dossiers/DISS-9eaed058-ddea-203e-e044-00144f67d031/DISS-9eaed058-ddea-203e-e044-00144f67d031_DISS-9eaed058-ddea-203e-e044-00144f67d031.html. [237] All fields indicate that the registrant considers data
for all endpoints as conclusive but not sufficient for classification. [238] http://nanopartikel.info/cms/lang/en/Wissensbasis/Aluminiumoxide/template/element2Category2ContainerList?catTitle=Exposure&containerID=534&queryPath=/content/jahia/dana/ContentPage_3/Wissensbasis/Aluminiumoxide/element2Category2ContainerList/ContentContainer_534 [239] http://nanopartikel.info/cms/lang/en/Wissensbasis/Aluminiumoxide [240] Public
information available on:
http://apps.echa.europa.eu/registered/data/dossiers/DISS-9eb9b2bd-9dfd-0981-e044-00144f67d031/DISS-9eb9b2bd-9dfd-0981-e044-00144f67d031_DISS-9eb9b2bd-9dfd-0981-e044-00144f67d031.html. [241] Except for: Acute toxicity – dermal; Acute toxicity –
inhalation; Respiratory sensitization; Aspiration hazard; Reproductive toxicity;
Effects via lactation (data lacking), all other fields indicate that the registrant
considers data for all other endpoints as conclusive but not sufficient for
classification. [242] Public
information available on:
http://apps.echa.europa.eu/registered/data/dossiers/DISS-9ea4fafe-9d48-4fe0-e044-00144f67d031/DISS-9ea4fafe-9d48-4fe0-e044-00144f67d031_DISS-9ea4fafe-9d48-4fe0-e044-00144f67d031.html. [243] Except for the classification as self heating and except
for: Acute toxicity – dermal; Acute toxicity – inhalation; Respiratory
sensitization; Aspiration hazard; Reproductive toxicity; Effects via lactation
(data lacking), all other fields indicate that the registrant considers data
for all other endpoints as conclusive but not sufficient for classification. [244] http://nanopartikel.info/cms/lang/en/Wissensbasis/Eisen/template/element2Category2ContainerList?catTitle=Exposure&containerID=396&queryPath=/content/jahia/dana/ContentPage_3/Wissensbasis/Eisen/element2Category2ContainerList/ContentContainer_396 [245] Public
information available on:
http://apps.echa.europa.eu/registered/data/dossiers/DISS-a217355e-db00-127d-e044-00144f67d031/DISS-a217355e-db00-127d-e044-00144f67d031_DISS-a217355e-db00-127d-e044-00144f67d031.html. [246] Bulk form: Except for: Respiratory sensitization; Aspiration
hazard; Effects via lactation; carcinogenicity; hazardous to the ozone layer
(data lacking), all other fields indicate that the registrant considers data
for all other endpoints as conclusive but not sufficient for classification;
Nanoform: except for: Skin corrosion / irritation; Germ cell mutagenicity; Hazardous
to the aquatic environment (both acute/short-term and long-term) (conclusive
but not sufficient for classification), the registrant indicates that data for
all other endpoints are lacking. [247] http://nanopartikel.info/cms/lang/en/Wissensbasis/Cerdioxid/template/element2Category2ContainerList?catTitle=Exposure&containerID=67&queryPath=/content/jahia/dana/ContentPage_3/Wissensbasis/Cerdioxid/element2Category2ContainerList/ContentContainer_67 [248] Public
information available on: http://apps.echa.europa.eu/registered/data/dossiers/DISS-97d7012e-917c-6fad-e044-00144f67d031/DISS-97d7012e-917c-6fad-e044-00144f67d031_DISS-97d7012e-917c-6fad-e044-00144f67d031.html. [249] Except for: Acute toxicity – dermal; Respiratory
sensitization; Aspiration hazard; Effects via lactation; carcinogenicity;
hazardous to the ozone layer (data lacking), all other fields indicate that the
registrant considers data for all other endpoints as conclusive but not
sufficient for classification. [250] http://nanopartikel.info/cms/lang/en/Wissensbasis/Zirkoniumdioxid/template/element2Category2ContainerList?catTitle=Exposure&containerID=591&queryPath=/content/jahia/dana/ContentPage_3/Wissensbasis/Zirkoniumdioxid/element2Category2ContainerList/ContentContainer_591 [251] Public
information available on: http://apps.echa.europa.eu/registered/data/dossiers/DISS-97d78296-bd48-13fd-e044-00144f67d031/DISS-97d78296-bd48-13fd-e044-00144f67d031_DISS-97d78296-bd48-13fd-e044-00144f67d031.html;
http://apps.echa.europa.eu/registered/data/dossiers/DISS-9876be4a-cbe0-274b-e044-00144f67d031/DISS-9876be4a-cbe0-274b-e044-00144f67d031_DISS-9876be4a-cbe0-274b-e044-00144f67d031.html. [252] For both substances, all fields indicate that the
registrant considers data for all endpoints as conclusive but not sufficient
for classification. [253] This list is not exhaustive. In addition, there are also
reaction masses between different oxides, which are not listed here. [254] http://www.observatorynano.eu/project/filesystem/files/Construction%20-%20Adhesive%20%20Sealants%20-%202010.pdf [255] Public
information available on: http://apps.echa.europa.eu/registered/data/dossiers/DISS-97d91307-32ca-6360-e044-00144f67d031/DISS-97d91307-32ca-6360-e044-00144f67d031_DISS-97d91307-32ca-6360-e044-00144f67d031.html. [256] Both bulk and nanoform: Except for: Respiratory
sensitization; Aspiration hazard; Effects via lactation (data lacking), all
other fields indicate that the registrant considers data for all other
endpoints as conclusive but not sufficient for classification. [257] http://www.efsa.europa.eu/en/efsajournal/pub/2318.htm [258] The share of particles with a size less than 100 nm in food
grade calcium carbonate is estimated at less than 1%. [259] Public
information available on:
http://apps.echa.europa.eu/registered/data/dossiers/DISS-9ea8a704-db22-007b-e044-00144f67d031/DISS-9ea8a704-db22-007b-e044-00144f67d031_DISS-9ea8a704-db22-007b-e044-00144f67d031.html. [260] Except for: Respiratory sensitization; Effects via
lactation; Carcinogenicity (data lacking), all other fields indicate that the
registrant considers data for all other endpoints as conclusive but not
sufficient for classification. [261] http://nanopartikel.info/cms/lang/en/Wissensbasis/Titannitrid [262] http://www.efsa.europa.eu/en/efsajournal/pub/888.htm [263] http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=OJ:L:2011:012:0001:0089:EN:PDF;
for scientific opinion, see: http://www.efsa.europa.eu/en/scdocs/doc/cef_op_ej888-890_21stlist_en,3.pdf [264] http://nanopartikel.info/cms/lang/en/Wissensbasis/Titannitrid/template/element2Category2ContainerList?catTitle=Exposure&containerID=768&queryPath=/content/jahia/dana/ContentPage_3/Wissensbasis/Titannitrid/element2Category2ContainerList/ContentContainer_768 [265] Note that alloys are not substances but special mixtures
for the purpose of REACH. [266] Engineered Nanoparticles - Review of Health and
Environmental Safety (ENRHES), http://ihcp.jrc.ec.europa.eu/whats-new/enhres-final-report,
p. 354;
http://nanopartikel.info/cms/lang/en/Wissensbasis/gold/template/element2Category2ContainerList?catTitle=Exposure&containerID=692&queryPath=/content/jahia/dana/ContentPage_3/Wissensbasis/gold/element2Category2ContainerList/ContentContainer_692. [267] Public
information available on:
http://apps.echa.europa.eu/registered/data/dossiers/DISS-9d92ea78-89c7-2334-e044-00144f67d249/DISS-9d92ea78-89c7-2334-e044-00144f67d249_DISS-9d92ea78-89c7-2334-e044-00144f67d249.html. [268] Except for the classification as Aquatic Chronic 1 H410:
Very toxic to aquatic life with long lasting effects and except for:
Reproductive toxicity; Effects via lactation, Carcinogenicity; Hazardous to the
aquatic environment (acute/short-term) (data lacking), all other fields
indicate that the registrant considers data for all other endpoints as conclusive
but not sufficient for classification. [269] Engineered Nanoparticles - Review of Health and
Environmental Safety (ENRHES), http://ihcp.jrc.ec.europa.eu/whats-new/enhres-final-report.
p. 354; http://nanopartikel.info/cms/lang/en/Wissensbasis/Silber/template/element2Category2ContainerList?catTitle=Exposure&containerID=192&queryPath=/content/jahia/dana/ContentPage_3/Wissensbasis/Silber/element2Category2ContainerList/ContentContainer_192. [270] Engineered Nanoparticles - Review of Health and
Environmental Safety (ENRHES), http://ihcp.jrc.ec.europa.eu/whats-new/enhres-final-report,
p. 358. [271] http://ec.europa.eu/health/scientific_committees/emerging/docs/scenihr_q_027.pdf [272] Engineered Nanoparticles - Review of Health and
Environmental Safety (ENRHES), http://ihcp.jrc.ec.europa.eu/whats-new/enhres-final-report.
p. 358. [273] ObservatoryNano http://www.observatorynano.eu/project/document/63/;
http://www.observatorynano.eu/project/document/66/ [274] http://www.rivm.nl/bibliotheek/rapporten/340370001.pdf,
p. 22. [275] Nucleus to nucleus in a crystalline structure of C60
molecules. [276] EU-OSHA, Workplace exposure to nanoparticles,
Luxembourg, 2009. Available at: http://osha.europa.eu/en/publications/literature_reviews/workplace_exposure_to_nanoparticles/view;
Engineered Nanoparticles - Review of Health and Environmental Safety (ENRHES), http://ihcp.jrc.ec.europa.eu/whats-new/enhres-final-report,
p. 353; http://nanopartikel.info/cms/lang/en/Wissensbasis/Fullerene/template/element2Category2ContainerList?catTitle=Exposure&containerID=353&queryPath=/content/jahia/dana/ContentPage_3/Wissensbasis/Fullerene/element2Category2ContainerList/ContentContainer_353. [277] In principle, carbon nanotubes are a special type of
carbon nanofibres. However, sometimes the term “carbon nanotubes” is used to
characterise the thinner carbon fibres, whereas the term “carbon nanofibres” is
used for the thicker variants. [278] Public
information available on:
http://apps.echa.europa.eu/registered/data/dossiers/DISS-b281d1a0-c6d8-5dcf-e044-00144f67d031/DISS-b281d1a0-c6d8-5dcf-e044-00144f67d031_DISS-b281d1a0-c6d8-5dcf-e044-00144f67d031.html. [279] Except for: Respiratory sensitization; Effects via
lactation; hazardous to the ozone layer (data lacking), all other fields
indicate that the registrant considers data for all endpoints as conclusive but
not sufficient for classification. [280] http://apps.echa.europa.eu/registered/data/dossiers/DISS-abda73cd-a2cd-3801-e044-00144f67d249/DISS-abda73cd-a2cd-3801-e044-00144f67d249_DISS-abda73cd-a2cd-3801-e044-00144f67d249.html [281] Except for the classification as Eye Irrit. 2 H319:
Causes serious eye irritation; and STOT Single Exp. 3 H335: May cause
respiratory irritation., and except for: Respiratory sensitization; Aspiration
hazard; Reproductive toxicity; Effects via lactation; hazardous to the ozone
layer (data lacking); and carcinogenicity (inconclusive), all other fields
indicate that the registrant considers data for all other endpoints as conclusive
but not sufficient for classification. [282] EU-OSHA, Workplace exposure to nanoparticles,
Luxembourg, 2009. Available at: http://osha.europa.eu/en/publications/literature_reviews/workplace_exposure_to_nanoparticles/view;
Engineered Nanoparticles - Review of Health and Environmental Safety (ENRHES), http://ihcp.jrc.ec.europa.eu/whats-new/enhres-final-report,
p. 353;
http://nanopartikel.info/cms/lang/en/Wissensbasis/kohlenstoffnanoroehrchen/template/element2Category2ContainerList?catTitle=Exposure&containerID=165&queryPath=/content/jahia/dana/ContentPage_3/Wissensbasis/kohlenstoffnanoroehrchen/element2Category2ContainerList/ContentContainer_165. [283] Donaldson, K., Murphy, F. A., Duffin, R., Poland, C. A.,
'Asbestos, carbon nanotubes and the pleural mesothelium: a review and the
hypothesis regarding the role of long fibre retention in the parietal pleura,
inflammation and mesothelioma', Particle & Fibre Toxicology, Vol. 7, p. 5,
2010. [284] http://www.marketresearch.com/Future-Markets-Inc-v3760/Carbon-Nanotubes-Nanofibers-Fullerenes-POSS-6542959/ [285] Möhlmann, C. et al., “Exposure to carbon nano-objects in
research and industry”, INRS Occupational Health Research Conference 2011
“Risks associated with nanoparticles and nanomaterials”, April 2011, Conference
proceedings, Session II, p. 64. [286] Public
information available on: http://apps.echa.europa.eu/registered/data/dossiers/DISS-76fd8ce3-be46-5f12-e044-00144f26965e/DISS-76fd8ce3-be46-5f12-e044-00144f26965e_DISS-76fd8ce3-be46-5f12-e044-00144f26965e.html;
http://apps.echa.europa.eu/registered/data/dossiers/DISS-9ead7c63-de5e-523a-e044-00144f67d031/DISS-9ead7c63-de5e-523a-e044-00144f67d031_DISS-9ead7c63-de5e-523a-e044-00144f67d031.html;
http://apps.echa.europa.eu/registered/data/dossiers/DISS-9e9e2f65-87c3-4085-e044-00144f67d031/DISS-9e9e2f65-87c3-4085-e044-00144f67d031_DISS-9e9e2f65-87c3-4085-e044-00144f67d031.html. [287] Except for the classification Carc. 2H351: Suspected of
causing cancer; Route of exposure: Inhalation.in one of three dossiers: and
except for Effects via lactation (all three dossiers data lacking) and for Acute
toxicity – dermal; Aspiration hazard; Reproductive toxicity; Germ cell
mutagenicity; hazardous to the ozone layer (all one out of three dossiers: data
lacking), all other fields on health and environmental hazards in the three
dossiers indicate that the registrants consider data for all other endpoints as
conclusive but not sufficient for classification. [288] Note that experimental studies are typically conducted
with high doses. [289] International Agency for Research on Cancer – IARC, IARC
Monographs on the Evaluation of Carcinogenic Risks to Humans - Carbon Black,
Titanium Dioxide, and Talc, Volume 93, (2010). Available at : http://monographs.iarc.fr/ENG/Monographs/vol93/index.php. [290] Hodgson, J.T. and Jones, R.D. 1985, A mortality study of
carbon black workers employed at five United Kingdom factories between 1947 and
1980, Archives of Environmental Health, vol. 40, pp. 261-268. [291] Sorahan, T., Hamilton, L., van Tongeren, M., Gardiner,
K. and Harrington, J.M. 2001, A cohort mortality study of U.K. carbon black
workers, 1951-1996, Am J Ind Med, vol. 39, pp. 158-170. [292] Engineered Nanoparticles - Review of Health and
Environmental Safety (ENRHES), http://ihcp.jrc.ec.europa.eu/whats-new/enhres-final-report,
executive summary p. xiv. [293] International Agency for Research on Cancer,
http://www.iarc.fr/. [294] http://monographs.iarc.fr/ENG/Monographs/vol93/mono93.pdf,
p. 190. [295] Note that IARC classified carbon
black as a possible carcinogen to humans only based on results from
experimental studies. [296] EU-OSHA, Workplace exposure to nanoparticles,
Luxembourg, 2009. Available at: http://osha.europa.eu/en/publications/literature_reviews/workplace_exposure_to_nanoparticles/view. [297] http://nanopartikel.info/cms/lang/en/Wissensbasis/CarbonBlack/template/element2Category2ContainerList?catTitle=Exposure&containerID=552&queryPath=/content/jahia/dana/ContentPage_3/Wissensbasis/CarbonBlack/element2Category2ContainerList/ContentContainer_552 [298] Niwa, Y., Hiura, Y., Murayama, T., Yokode, M., Iwai, N.,
´Nano-sized carbon black exposure exacerbates atherosclerosis in LDL-receptor
knockout mice´, Circulation Journal: Official Journal of the Japanese
Circulation Society, 71, 2007, 1157-1161. [299] Last six uses: http://nanopartikel.info/cms/lang/en/Wissensbasis/CarbonBlack. [300] As part of the rubber matrix. [301] Nevertheless, in most cases, the monomers the polymer
consists of must be registered. See REACH Regulation, Article 6(3),
http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=OJ:L:2007:136:0003:0280:en:PDF.
[302] http://nanopartikel.info/cms/lang/en/Wissensbasis/Cellulose [303] http://en.wikipedia.org/wiki/Quantum_dot [304] http://bccresearch.blogspot.com/2011/06/global-market-for-quantum-dots-to-grow.html [305] http://www.ias.ac.in/matersci/bmsapr2006/133.pdf [306] http://www.observatorynano.eu/project/filesystem/files/Briefing%20No.23%20Nanotechnology%20in%20Automotive%20Tyres.pdf [307] http://www.marketresearch.com/search/results.asp?query=nanoclays&submit1=Go [308] http://www.reach-centrum.org/en/consortiumslt/consortia-under-reach/organoclays-reach-consortium.aspx [309] http://www.bund.net/nc/themen_und_projekte/nanotechnologie/nanoproduktdatenbank/produktsuche/ [310] http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=COM:2008:0366:FIN:en:PDF [311] REACH: Regulation (EC) No 1907/2006 concerning the
Registration, Evaluation, Authorisation and Restriction of Chemicals. [312] Regulation (EC) No 1272/2008 on Classification,
Labelling and Packaging of substances and mixtures. [313] http://ec.europa.eu/environment/chemicals/reach/pdf/nanomaterials.pdf [314] http://ec.europa.eu/environment/chemicals/reach/pdf/classif_nano.pdf [315] http://iuclid.echa.europa.eu/index.php?fuseaction=home.documentation#technicalmanual [316] http://www.oecd.org/officialdocuments/displaydocumentpdf/?cote=env/jm/mono(2010)46&doclanguage=en [317] NanoDE-Report
2009- Status quo der Nanotechnologie in Deutschland (http://www.bmbf.de/pub/nanode_report_2009_en.pdf) [318] Note that these are not necessarily covered by the
Definition of Commission Recommendation 2011/696/EU. [319] Engineered Nanoparticles - Review of Health and
Environmental Safety (ENRHES), http://ihcp.jrc.ec.europa.eu/whats-new/enhres-final-report. [320] European Agency for Safety and Health at Work, http://osha.europa.eu/en/front-page/view. [321] http://ec.europa.eu/environment/chemicals/nanotech/pdf/study_inventory.pdf [322] Regulation (EC) No 1907/2006 of the European Parliament
and of the Council of 18 December 2006 concerning the Registration, Evaluation,
Authorisation and Restriction of Chemicals (REACH), OJ L 396, 30.12.2006, p. 1. [323] http://echa.europa.eu/web/guest/information-on-chemicals/registered-substances [324] For more details, see Appendix 7. [325] November 2011: NLCG counts 37 members, including ISO,
CEN, IEC, OECD committees and working parties, CIPM and VAMAS; the European
Commission is represented through liaison officers from the EC Joint Research
Centre (JRC)). [326] The 6-monthly liaison reports are publicly available on
the ISO/TC 229 livelink website (http://isotc.iso.org/livelink/livelink/open/tc229). [327] ISO/TS 10798:2011 'Nanotechnologies – Characterization
of single-wall carbon nanotubes using scanning electron microscopy and energy
dispersive X-ray spectrometry analysis'. [328] EN ISO 10801:2010 'Nanotechnologies – Generation of
metal nanoparticles for inhalation toxicity testing using the
evaporation/condensation method'. [329] EN ISO 10808:2010 'Nanotechnologies – Characterization
of nanoparticles in inhalation exposure chambers for inhalation toxicity
testing'. [330] ISO/TS 10867:2010 'Nanotechnologies – Characterization
of single-wall carbon nanotubes using near infrared photoluminescence
spectroscopy'. [331] ISO/TS 80004-1:2010 'Nanotechnologies – Vocabulary –
Part 1: Core terms'. [332] CEN ISO/TS 27687: 2008 ‘Nanotechnologies – Terminology
and definitions for nano-objects – Nanoparticle, nanofibre and nanoplate’. [333] ISO/TS 80004-3:2010 'Nanotechnologies – Vocabulary –
Part 3: Carbon nano-objects'. [334] ISO/TS 80004-7:2011 ' Nanotechnologies – Vocabulary –
Part 7: Diagnostics and therapeutics for healthcare'. [335] EN ISO 29701: 2010 'Nanotechnologies – Endotoxin test on
nanomaterial samples for in vitro systems – Limulus amebocyte lysate (LAL)
test'. [336] ISO/TS 11251:2010 ' Nanotechnologies – Characterization
of volatile components in single-wall carbon nanotube samples using evolved gas
analysis/gas chromatograph-mass spectrometry'. [337] ISO/TR 12885: 2008 ‘Nanotechnologies – Health and safety
practices in occupational settings relevant to nanotechnologies’. [338] ISO/TR 13121:2011 'Nanotechnologies -- Nanomaterial risk
evaluation'. [339] ISO/TR 12802:2010 ' Nanotechnologies – Model taxonomic
framework for use in developing vocabularies – Core concepts'. [340] ISO/TR 11360: 2010 'Nanotechnologies – Methodology for
the classification and categorization of nanomaterials'. [341] ISO/TS 10868:2011 ' Nanotechnologies -- Characterization
of single-wall carbon nanotubes using ultraviolet-visible-near infrared
(UV-Vis-NIR) absorption spectroscopy'. [342] ISO/TS 80004-4:2011 'Nanotechnologies – Vocabulary –
Part 4: Nanostructured materials'. [343] ISO/TS 11308:2011 'Nanotechnologies -- Characterization
of single-wall carbon nanotubes using thermogravimetric analysis'. [344] ISO/TS 11888:2011 'Nanotechnologies -- Characterization
of multiwall carbon nanotubes -- Mesoscopic shape factors'. [345] ISO/TS 12805:2011 'Nanotechnologies -- Materials
specifications -- Guidance on specifying nano-objects'. [346] ISO/TS 13278:2011 'Nanotechnologies -- Determination of
elemental impurities in samples of carbon nanotubes using inductively coupled
plasma mass spectrometry'. [347] ISO/TS 80004-5:2011 'Nanotechnologies -- Vocabulary --
Part 5: Nano/bio interface'. [348] IEC/PAS 62565-2-1 'Nanomanufacturing - Material
specifications - Part 2-1: Single-wall carbon nanotubes - Blank detail
specification'. [349] IEC 62624 Test methods for measurement of electrical
properties of carbon nanotubes. [350] ISO TS 80004-1:2010 Nanotechnologies – Vocabulary – Part
1: Core terms. [351] Some of these terms were used in the definition, for
regulatory purposes, of the term nanomaterial by the EC. [352] CEN ISO/TS 27687: 2008 ‘Nanotechnologies – Terminology
and definitions for nano-objects – Nanoparticle, nanofibre and nanoplate’. [353] ISO/TS 80004-3:2010 'Nanotechnologies – Vocabulary –
Part 3: Carbon nano-objects'. [354] ISO TS 80004-4:2011 Nanotechnologies – Vocabulary – Part
4: Nanostructured Materials. [355] ISO/TS 80004-5:2011 'Nanotechnologies -- Vocabulary --
Part 5: Nano/bio interface'. [356] ISO/TS 10798:2011 'Nanotechnologies – Characterization
of single-wall carbon nanotubes using scanning electron microscopy and energy
dispersive X-ray spectrometry analysis'. [357] ISO/TS 10867:2010 'Nanotechnologies – Characterization
of single-wall carbon nanotubes using near infrared photoluminescence
spectroscopy'. [358] ISO/TS 11251:2010 ' Nanotechnologies – Characterization
of volatile components in single-wall carbon nanotube samples using evolved gas
analysis/gas chromatograph-mass spectrometry'. [359] ISO/TS 10868:2011 ' Nanotechnologies -- Characterization
of single-wall carbon nanotubes using ultraviolet-visible-near infrared
(UV-Vis-NIR) absorption spectroscopy'. [360] ISO/TS 11308:2011 'Nanotechnologies -- Characterization
of single-wall carbon nanotubes using thermogravimetric analysis'. [361] ISO/TS 11888:2011 'Nanotechnologies -- Characterization
of multiwall carbon nanotubes -- Mesoscopic shape factors'. [362] ISO/TS 13278:2011 'Nanotechnologies -- Determination of
elemental impurities in samples of carbon nanotubes using inductively coupled
plasma mass spectrometry'. [363] IEC/PAS 62565-2-1 'Nanomanufacturing - Material
specifications - Part 2-1: Single-wall carbon nanotubes - Blank detail
specification'. [364] IEC 62624 Test methods for measurement of electrical
properties of carbon nanotubes. [365] EN ISO 10801:2010 'Nanotechnologies – Generation of
metal nanoparticles for inhalation toxicity testing using the evaporation/condensation
method'. [366] EN ISO 10808:2010 'Nanotechnologies – Characterization
of nanoparticles in inhalation exposure chambers for inhalation toxicity
testing'. [367] ISO/IEC 17025:2005 General requirements for the
competence of testing and calibration laboratories. [368] Certification of equivalent spherical diameters of
silica nanoparticles in water, ERM-FD100, A. Braun, K. Franks, V. Kestens, G.
Roebben, A. Lamberty, T. Linsinger, Report EUR 24620 EN, European Union,
Luxembourg, ISBN 978-92-79-18676-9, 2011.