Table Of ContentNANOENGINEERING
Global Approaches to Health
and Safety Issues
Editedby
PATRICIA I. DOLEZ
CTT Group, St-Hyacinthe, QC, Canada
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LIST OF CONTRIBUTORS
Rickard Arvidsson
DivisionofEnvironmentalSystemsAnalysis,DepartmentofEnergyandEnvironment,Chalmers
University of Technology, Gothenburg,Sweden
Christof Asbach
Institut fu€r Energie-und Umwelttechnik e.V. (IUTA), Air Quality&Filtration Department,
Duisburg, North Rhine-Westphalia,Germany
Jacques Xavier Bouillard
INERIS, Verneuil-en-Halatte,France
Jessica R. Child
RTI International, Research Triangle Park, NC, USA
MaximilienDebia
DepartmentofEnvironmentalandOccupationalHealth,SchoolofPublicHealth,Universit(cid:2)ede
Montr(cid:2)eal,Montr(cid:2)eal, Qu(cid:2)ebec, Canada
Paul De Hert
Law,Science,Technology&SocietyStudies(LSTS)VrijeUniversiteitBrussel,Brussels,Belgium
Patricia I. Dolez
CTT Group, St-Hyacinthe, QC, Canada
June Freeland
DepartmentofSafetyServicesandOccupationalHealth,UniversityofStrathclyde,Glasgow,UK
Raphaël Gellert
Law,Science,Technology&SocietyStudies(LSTS)VrijeUniversiteitBrussel,Brussels,Belgium
FrançoisGensdarmes
InstitutdeRadioprotectionetdeSu^ret(cid:2)eNucl(cid:2)eaire(IRSN),PSN-RES,SCA,AerosolPhysicsand
Metrology Laboratory,Gif-sur-Yvette,France
Marco Giardiello
Departmentof Chemistry, University of Liverpool, Liverpool, UK
Brian Haydon
CSAGroup, Toronto, ON,Canada
Mathew Hull
Woodrow Wilson International Centerfor Scholars, Washington, DC, USA
Jutta Jahnel
Karlsruhe Institute of Technology, Institute for Technology Assessmentand SystemsAnalysis
(ITAS), Karlstrasse, Germany
Todd Kuiken
Woodrow Wilson International Centerfor Scholars, Washington, DC, USA
xxi
xxii ListofContributors
GeorgesA.Legault
FacultyofLaw,Institutinterdisciplinaired’innovationtechnologique,Universit(cid:2)edeSherbrooke,
Sherbrooke, QC, Canada
Neill Liptrott
Department of Molecular and Clinical, Pharmacology, University of Liverpool, Liverpool, UK
EugenioMantovani
Law,Science,Technology&SocietyStudies(LSTS)VrijeUniversiteitBrussel,Brussels,Belgium
Tom O. McDonald
Department of Chemistry, Universityof Liverpool, Liverpool, UK
Sean McGinnis
Woodrow Wilson International Center forScholars, Washington, DC, USA
HeatherV.A.McShane
Department of Natural Resource Sciences,McGill University, Quebec, Canada
Darren Moss
Department of Molecular and Clinical, Pharmacology, University of Liverpool, Liverpool, UK
Mariko Ono-Ogasawara
Work EnvironmentResearch Group, Japan NationalInstitute of Occupational Safety and
Health,Tama-ku,Kawasaki, Kanagawa, Japan
Claude Ostiguy
DepartmentofEnvironmentalandOccupationalHealth,SchoolofPublicHealth,Universit(cid:2)ede
Montr(cid:2)eal,Montr(cid:2)eal,Qu(cid:2)ebec,Canada;InstitutderechercheRobert-Sauv(cid:2)eensant(cid:2)eetens(cid:2)ecurit(cid:2)e
dutravail,Montr(cid:2)eal,Qu(cid:2)ebec, Canada
Andrew Owen
Department of Molecular and Clinical, Pharmacology, University of Liverpool, Liverpool, UK
JohanePatenaude
FacultyofMedicineandHealthSciences,Institutinterdisciplinaired’innovationtechnologique,
Universit(cid:2)e de Sherbrooke, Sherbrooke, QC, Canada
S. Pavel
Department of Dermatology, Charles University, Pilsen, Czech Republic
MarinaE.Quadros
Woodrow Wilson International Center forScholars, Washington, DC, USA
Steve Rannard
Department of Chemistry, Universityof Liverpool, Liverpool, UK
ChristieM. Sayes
RTI International, ResearchTrianglePark, NC,USA
Marco Siccardi
Department of Molecular and Clinical, Pharmacology, University of Liverpool, Liverpool, UK
T. Smijs
Centrefor OpticalDiagnostics and Therapy, Department of Radiotherapy, Erasmus Medical
Centre,Rotterdam, The Netherlands
ListofContributors xxiii
GeoffreyI. Sunahara
Departmentof NaturalResource Sciences, McGill University, Quebec, Canada
Danielle Tapin
FacultyofMedicineandHealthSciences,Institutinterdisciplinaired’innovationtechnologique,
Universit(cid:2)e deSherbrooke,Sherbrooke, QC,Canada
MichaelG.Tyshenko
Institute of Population Health,University of Ottawa, Ottawa, ON,Canada
David B.Warheit
DuPont HaskellLaboratory, Newark, DE, USA
PREFACE
Nanotechnology has emerged as the forefront of science with its multidisciplinary and
diverse scope of research and applications. Nanoengineering materials such as carbon
nanotubes and fullerenes with their novel and extraordinary properties have captured a
great deal of public interest and imagination over the past 20years.
Datedbackin1986,EricDrexlerpopularizedanideathat“thecomingeraofnano-
technology” would radically change our world. The U.S. National Science and Tech-
nology Council in 2000 indicated that “The effect of nanotechnology on the health,
wealth, and lives of people could be at least as significant as the combined influences
of microelectronics, medical imaging, computer-aided engineering, and man-made
polymers developed in this century.” However, some visionaries warned that with its
omni power nanotechnology could pose a great risk and danger to humanity and the
environment at large.
At the 2nd International Congress of Nanotechnology (ICNT) in 2005, I had the
privilegeofchairingthefirstSymposiumontheEnvironmentalHealthandSafetyImpact
of Nanotechnology (“nanoEHS”). The conference was a tribute to Prof. Richard
Smalley, a Nobel laureate for the discovery of fullerenes, who passed away at the age
of 62 due to leukemia. Prof. Smalley left a remarkable legacy through his devotion to
science even when it put his own health at risk with constant exposure to fullerenes in
his laboratory without adequate protection.
Overthepast10years,ithasbeenacontroversialtopictodiscussnanoEHS.Whilea
majority of researchers favored an increased funding for nanoEHS, some expressed
concernthatthestudyontheenvironmentalandhealthandsafetyimpactwouldimpede
the momentum of the research and commercial applications of nanotechnology.
Thanks to consensus among researchers that requested more funding for nanoEHS,
the U. S. National Nanotechnology Initiative (NNI) research dedicated to nanoEHS
grewsubstantiallyfrom$25millioninFY2005toanestimated$121.1millionrequested
for FY 2014. Between FY 2005 and FY 2014 the National Nanotechnology Initiative
will have invested $750million in research with the primary function of understanding
EHS issues.
Since its founding in 2003, the International Association of Nanotechnology has
recognizedtheimportantroleofenvironmental,healthandsafetypracticesasafounda-
tionforasafeandbeneficialNanotechnology.Thenovelphysicochemicalandbiological
propertiesthatcanmakenanotechnologyapplicationssoexciting,alsorequireextensive
studies on any effects on product safety, effectiveness, or other attributes.
xxv
xxvi Preface
This book is a timely review on the global effort on the health and safety issues of
nanoengineeringmaterials,devices,andstructures.Thebookbringstogethernanotech-
nology researchers from around the world to discuss a wide spectrum of topics under
three major sections:
Section1startswithageneralintroductiononnaturalandengineerednanomaterials
with various definitions, classifications, and synthesis routes and applications. Routes of
exposure to nanomaterials throughout their entire life cycle are described, in addition
to metrology and methods of detection and characterization from the perspective of
industrial processes and hygiene evaluation.
Asengineerednanomaterialshavegainedastrongfootholdinalargenumberofcon-
sumerproducts,humanshavebeenexposedtonanomaterialsthroughintentionalintake
such as food and medicines, and unintentional such as inhalation of nanoparticles in
workplace settings. As a result, it is important to assess the long-term exposure and to
evaluate the toxicological and biological impact of nanomaterials and their safety.
Nano-bio interactions and nanotoxicity in in vitro models is described and discussed.
Asacasestudy,combustiblenanopowderswhichhaveahighlikelihoodofexplosion
becauseoftheirhighspecificsurfaceandtheirlowthresholdlimitsofignitionenergycon-
ditionsaredescribed.Itisinterestingtoobservethattheexplosionseverityofcombustible
nanopowders is governed by their primary particle size and their tendency to agglom-
erate/coagulate, which significantly differs from the behavior of micropowders.
Section2focusesonnanomedicineandconsumerproducts.AccordingtotheProject
on Emerging Nanotechnologies at the Woodrow Wilson International Center for
Scholars, consumer products containing nanomaterials have grown from 54 in 2005 to
well over 1500 products in 2013. This first-of-its-kind consumer products inventory is
one of the most widely cited inventories of nanotechnology consumer products.
However, it has been rightfully criticized due to its lack of scientific data, which should
have been based on exposure, toxicity, and life cycle implications of nanomaterials.
The NNI framework for nanoEHS research strategy integrates several important
conceptsdrisk assessment and product life cycle stagesdinto the basic and applied
research to understand the EHS impactsof nanomaterials. In this book, lifecycle assess-
ment and risk assessment of manufactured nanomaterials, environmental perspectives,
and risk management and surveillance of nanomaterials are discussed. Risk assessment
takesintoaccountthelifecycleofnanomaterials,whichoncereleasedintotheenviron-
mentmayundergotransformationbyenvironmentalconditionssuchastemperatureand
salinity,andthepresenceofco-contaminants.Thesetransformations mayaltertheform
ofthenanomaterialstowhichhumansandecosystemsareexposedandwhicharetrans-
ported through the environment.
Theethicalissuesofnanoengineeringareascientificquestforstudyingthelong-term
impact of nanomaterials on the economic development, the “have and the have-not”
and societal implications.
Preface xxvii
The EU regulation of nanotechnology, which is based on the precautionary
approach, serves as a starting point toward regulating nanomaterials in the industrial
applications. A case study involving nano-sized titanium dioxide in sunscreens is high-
lightedasanexampletoframethediscussionontheimpactoftheenvironmental,health
and safety of a new nanomaterial product in the marketplace.
Section3isdevotedtooccupationalaspectswiththepotentialworkplaceexposureto
manufactured and nonmanufactured nanomaterials in the research laboratories and
manufacturing industrial settings. While risk assessment is a primarily evidence-based
process to evaluate public health and environmental issues of concern, it has become a
dominant policy tool for informing regulatory and technological decisions and setting
priorities for research and funding. However, risk assessment is not always universally
accepted, as it depends on the sociocultural and regulatory contexts of the issues. As a
result,aresourcetoolboxandasetofgoodpracticesarepresentedaspracticalguidelines
which include intrinsic safety, engineering controls, administrative procedures, and per-
sonal protective equipment (PPE).
Workforce training safety awareness among nanotechnology workers and good
emergency plans are essential constituents of the prevention program. Even where
engineeringcontrolsandsafetysystemsofworkareapplied,somehazardsmightremain.
Inthat context,PPE plays an importantrole in theriskmanagementtoolbox underthe
precautionary principle adopted by several H&S agencies worldwide.
While progress has been made in understanding biological responses to engineered
nanomaterials,thefullconsequencesofoccupationalexposureareunknown.Toaddress
this, national and international efforts have been made to provide guidance using both
new and existing regulations to support research and development to limit and prevent
workerexposure.Lastly,acasestudyinvolvingcarbonnanotubescomparesdifferentas-
pects covered by these section chapters, in particular their potential interaction with
workers during their entire life cycle.
ThisbookpresentsareviewoftheglobaleffortinstudyingEHS,whichisacomplex
and an unchartered territory. After all, one of the hallmarks of science is to study and
explore theunknown.Exploring theunknown furthers ourunderstanding of thewon-
ders of materials science, enabling us to make the best use of nanoengineering products
for the benefits of our society at large.
Icongratulatetheauthors,editor,andpublishersfortheirhardworkinenlightening
thereaderswiththelatestdevelopmentinglobalapproachestohealthandsafetyissuesof
nanotechnology.
Lloyd L. Tran
International Association of Nanotechnology,
Mountain View, California, USA
CHAPTER 1.1
fi
Nanomaterials De nitions,
fi
Classi cations, and Applications
Patricia I. Dolez
CTTGroup,St-Hyacinthe,QC,Canada
1. DEFINITIONS
According to the International Organization for Standardization (ISO), the prefix nano
referstoasizerangingapproximatelyfrom1to100nm[1].Asacomparison,thediam-
eter of a carbon atom is about 0.25nm, and the distance between carbon atoms is
0.15nm.Nanomaterialsarethuslargerthansingleatomsorevensmallgroupsofatoms.
Nature’sexamplesofnano-sizedobjectsincludeDNAmolecules,whichhaveadiameter
of 25nm, viruses, with the smallest identified one, parvovirus, being 25nm wide, and
proteins that are typically 10nm long.
Theuseofnanotechnologyisfarfrombeingnew.Forexample,itwasusedaround
2600BCindyestoimpartcolortofibersandfabrics[2].Anotherexamplecanbefound
inMiddleAgechurches,wherestainedglassartisansutilizednanoscopicscale(ornano-
scale) gold and silver particles to impart ruby red and deep yellow color to window
panels[3].AnotherexampleistheDamascussteelproducedbythetwelfthtotheeigh-
teenthcenturyMiddleEasternmetalsmiths,whichincludescementitenanowiresinside
carbonnanotubes[4].Atthattime,theyhadnowaytoobservethenanostructuresthey
created. More recently, carbon black has been employed since 1910 to reinforce tires,
withoutknowingthatitwastheinteractionbetweenrubberandthenanoscalecarbon
black particles that imparted the tires with increased hardness, strength, abrasion, and
tear resistance [5].
The first scientist to raise attention on nanotechnologies, even if the word was not
coined yet, was Richard Feynman. In a talk he gave in 1959 at the annual meeting of
theAmericanPhysicalSocietyentitled“There’splentyofroomatthebottomdAninvi-
tation to enter a new field of physics,” he challenged his fellow physicists to write the
entire24volumesoftheEncyclopediaBritannicaontheheadofapin[6].Healsooffered
a $1000 price to the first person who would build a 1/64-cubic inch working electrical
motor.Itmustbementionedthatthispricewasclaimednotlongafterwardbyastudent,
WilliamMcLellan,whoconstructedsuchamotorusingtheconventional,watch-making
design [7].
The word nanotechnology wasused forthefirst timein1974byNorio Taniguchi
in reference to machining and finishing dimensional tolerances for semiconductor
Nanoengineering ©2015ElsevierB.V.
ISBN978-0-444-62747-6,http://dx.doi.org/10.1016/B978-0-444-62747-6.00001-4 Allrightsreserved. 3
4 Nanoengineering
processes [8]. It is derived from the Greek word for dwarf and means a billionth of a
unit. However, it was only after the development of the scanning tunneling micro-
scopein1981byIBMresearchersGerdBinningandHeinrichRohrer[9]thatprogress
really kicked off; it was now possible to observe matter at the nanoscale. They were
awarded a Nobel Prize in physics in 1986 for this discovery, which takes advantage
of the quantum phenomenon exhibited by conductor and semiconductor materials
at the nanoscale. Then, fullerenes were discovered in 1985 by Harold Kroto, Robert
Curl, and Richard Smalley [10], who won a Nobel Prize in chemistry in 1996 for
this achievement. The first controlled growth of carbon nanotubes is attributed to
Sumio Lijima and his colleagues in 1991 [11].
Since that time, the use of nanoscale materials and structures in commercial prod-
ucts has largely increased. The worldwide market for nano-enabled products was
valued at US$22.9billion in 2013 [12]. It is expected to reach US$64.2billion by
2019, with a compound annual growth rate of 19.8% between 2014 and 2019. The
last update in 2013 of the Nanotechnology Consumer Products Inventory of the
Woodrow Wilson International Center for Scholars has identified 1628 commercial
nanoproducts, including 440 on the European market [13]. As knowledge about the
potential dangers of nanomaterials as well as the need for standardization in this new
field have increased too, efforts have been devoted to defining the terminology
used,evenifdifferencesexistbetweencountries.Forexample,accordingtoISO,nano-
materialsaredefinedasmaterialswithanyexternaldimensioninthenanoscaleorhaving
aninternalstructureorsurfacestructureinthenanoscale[14],thenanoscalereferringto
a size ranging approximately from 1 to 100nm [1]. On the other hand, the European
Commission’srecommendationonthedefinitionofnanomaterialreleasedin2011is“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
1e100nm” [15]. They provide for exceptions for specific cases when concerns exist
for environment, health, safety, or competitiveness, in which case the concentration
thresholdisreducedbelow50%,andforfullerenes,grapheneflakesandsinglewallcar-
bon nanotubes with one or more external dimensions below 1nm, which are consid-
ered nanomaterials regardless of concentration. Canada has also established its own
workingdefinitionofnanomaterials,whichare“anymanufacturedsubstanceorprod-
uctandanycomponentmaterial,ingredient,device,orstructure[.]ifitisatorwithin
the nanoscale in at least one external dimension, or has internal or surface structure at
thenanoscale,oritissmallerorlargerthanthenanoscaleinalldimensionsandexhibits
oneormorenanoscaleproperties/phenomena”[16].Thislastdefinitionallowsconsid-
ering materials that are larger or smaller than the nanoscale range if they exhibit the
properties or phenomena that are characteristic of the nanoscale dimension.
