Nanoparticles: Sources, Monitoring Methods, and Potential Health Impacts

Yevgen Nazarenko, Ph.D.,

Advisor and Mentors: Prof. Gediminas “Gedi” Mainelis,

Prof. Paul J. Lioy

Bioaerosol Research Laboratory

Department of Environmental Sciences

Rutgers, the State University of New Jersey

14 College Farm Road

New Brunswick, NJ 08901

Tel.: +1 (732) 470-0201

Fax: +1 (732) 932-8644

E-mail: yevgennazarenko@gmail.com

Research Collaborators: Huajun Zhen, M.S., Taewon Han, Ph.D., Leonardo Calderon, M.S.

Classification of Nanoparticles

Main Figure adapted from B. Nowack, T.D. Bucheli / Environmental Pollution 150 (2007) 5-22 http://www.aquadyntech.com/h2omolecule.jpg

0.3 nm

1 – 100 nm in Perspective

http://images.wikia.com/gcse/images/d/d5/Glucose.png http://www.pdbj.org/eprots/images/2ODJ/2ODJ1.jpg http://www.dreamstime.com/influenza-flu-virus-structure-thumb9252986.jpg

1 nm

Glucose

10 nm

100 nm

Influenza A Virus

Nano-sized Particles and Materials

http://covers.elsevier.com/tango2/large/9781455778621.jpg http://www.azonano.com/images/sales/ImageForSaleItem_321.jpg http://books.gigaimg.com/avaxhome/33/5b/000a5b33_medium.jpeg http://cache.jalopnik.com/assets/images/12/2005/05/nanotech.gif http://cloudfront.dailybooth.com/12/pictures/large/eeadb82edfce447e9727ee219b013413_23091167.jpg http://topicden.com/wp-content/uploads/2010/06/nanotech.jpg http://bir-consulting.com/images/Picture-of-the-day/JB-inside-box.jpg http://2.bp.blogspot.com/_fLp_r2HnoyI/Sp_BJfrf1gI/AAAAAAAAARo/Zx_gVzygFho/s400/Nanotechnology+in+the+center+of+public+debate. jpg

Under “Regulation of the European Parliament and of the Council on Cosmetic Products” “Nanomaterial" means an insoluble or biopersistant and intentionally manufactured material with one or more external dimensions, or an internal structure, on the scale from 1 to 100 nm.

The US National Nanotechnology Initiative (NNI) defines nanotechnology as “the understanding and control of matter at dimensions between approximately 1 and 100 nanometers, where unique phenomena enable novel applications” (National Science and Technology Council, 2007).

Nano-sized Particles and Materials

• Naturally occurring nanoparticles and nanostructures

• Engineered nanoparticles and nanostructures

• Nanoparticle-contaning or nanostructured larger particles, agglomerates

• Complex substances and materials without a concrete chemical or physico-chemical identity

http://www.newhavenindependent.org/index.php/archives/entry/exposed_to_nano_exhale/

More Specific Definition of Nano

Nano-object – material with one, two or three external dimensions in the size range of approximately 1 – 100 nm

Nanoplate – nano-object with one external dimension of 1 – 100 nm

Nanofiber – nano-object with two external dimensions of 1 – 100 nm

Nanotube – a hollow nanofiber

Nanorod – a solid nanofiber

Nanoparticle – nano-object with all of the three external dimensions of 1 – 100 nm

Nanomaterial – any kind of nano-objects in the pure form or incorporated into a larger matrix or substrate

ISO/TS 27687:2008

“Nanotechnologies – Terminology and definitions for nano-objects – Nanoparticle, nanofibre and nanoplate”

What do Nanomaterials look like?

Nanoparticles ≠ Nanomaterial

Nano-objects can exist both as free nanoparticles and their

agglomerates or attached to larger particles

Sample 1 Sample 2

What do Nanomaterials look like?

In-house Synthesized Pure Silver Nanoparticles

Sources of Nanoparticles in the Atmosphere

Biosphere;

Volcanic eruptions and other geological processes;

Road traffic – both diesel and petrol-fuelled vehicles;

Stationary combustion sources;

Industrial emissions including nanomaterial manufacturing;

Homogeneous nucleation (nucleation without homogeneous nucleation sites);

Sources of Nanoparticles in the Atmosphere

Los Angeles Smog

Buzea, C., Pacheco, I.I., Robbie, K. 2007. Nanomaterials and nanoparticles: Sources and toxicity. Biointerphases, 2(4): MR17-MR172; http://www.epa.gov/airtrends/aqtrnd04/pmreport03/pmunderstand_2405.pdf, Accessed 13, August 2012

Size Distribution and aerosol composition over Los Angeles during 2002-2003

Sources of Nanoparticles in the Atmosphere

VOCs are oxidized by O3, OH and NO3 etc., and the resulting gaseous products condense into (homogeneous nucleation) and onto (heterogeneous nucleation) particles.*

*Riipinen, I., Yli-Juuti, T., Pierce, J. R., Petaja, T., Worsnop, D. R., Kulmala, M., Donahue, N. M. 2012. The contribution of organics to atmospheric nanoparticle growth. Nature Geoscience: 5: 453–458.

Sources of Nanoparticles Indoors

Afshari A., Matson U., Ekberg L. E. 2005. Characterization of indoor sources of fine and ultrafine particles: a study conducted in a full-scale chamber Indoor Air 15 141-150

Nanomaterial emissions indoors from industrial processes including nanomaterial and nanotechnology-based product manufacturing – lead to occupational exposure

Nanomaterials in Terrestrial and Aquatic Environments

Batley, G. E., Kirby, J. K., McLaughlin, M. J. Fate and Risks of Nanomaterials in Aquatic and Terrestrial Environments. Accounts of Chemical Research: Online 3, July 2012. DOI: 10.1021/ar2003368.

Fate and Transformations of Nanomaterials in the Environments

Health Concerns of Nanomaterial Exposure

Example 1: graphite-derived carbon nanoparticles (median diameter 36 nm) were found to translocate from the respiratory system to the olfactory bulb of the rat central nervous system. The same effect was found for the manganese oxide nanoparticles (median diameter 30 nm) with resulting inflammatory changes*

At the nanoscale, toxicity and associated biological and health effects of chemically the same substance may differ substantially depending on its size distribution and structural state

*Elder A, Gelein R, Silva V, Feikert T, Opanashuk L, Carter J, et al. 2006. Translocation of Inhaled Ultrafine Manganese Oxide Particles to the Central Nervous System. Environmental Health Perspectives 114(8): 1172-1178; Buzea, C., Pacheco, I.I., Robbie, K. 2007. Nanomaterials and nanoparticles: Sources and toxicity. Biointerphases, 2(4): MR17-MR172;

Health Concerns of Nanomaterial Exposure

Example 2: following intranasal instillation, a more intense inflammation response resulted in mice exposed to 21-nm anatase/rutile nano-TiO2 compared to 5-nm anatase nano-TiO2.*

Differences in nanomaterial toxicity can be profound even for small variations of particle size, including within the 1 – 100 nm range:

*Grassian VH, Adamcakova-Dodd A, Pettibone JM, O'Shaughnessy PT, Thorne PS. 2007. Inflammatory response of mice to manufactured titanium dioxide nanoparticles: Comparison of size effects through different exposure routes. Nanotoxicology 1(3): 211-226; Buzea, C., Pacheco, I.I., Robbie, K. 2007. Nanomaterials and nanoparticles: Sources and toxicity. Biointerphases, 2(4): MR17-MR172.

Health Concerns of Nanomaterial Exposure

Differences and similarities between carbon nanotubes and asbestos fibers during mesothelial carcinogenesis: Shedding light on fiber entry mechanism

Cancer Science Volume 103, Issue 8, pages 1378-1390, 14 JUN 2012 DOI: 10.1111/j.1349-7006.2012.02326.x http://onlinelibrary.wiley.com/doi/10.1111/j.1349-7006.2012.02326.x/full#cas2326-fig-0001

Human

exposure to

nanomaterials is

associated with

potential

health risks;

Different routes

of this exposure

are possible,

e.g. ingestion,

dermal,

inhalation

Human Exposure to Nanoparticles

Nanotechnology Safety • Of benefit to all stakeholders

including developers and product manufacturers and the government;

• Essential for the public including the end consumers and workers subject to occupational exposure

• Crucial for environmental safety

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Nanotechnology Safety – in the US • 2011 NNI Environmental, Health, and

Safety (EHS) Research Strategy:

“a comprehensive approach to ensuring the safe, effective, and responsible development and use of nanotechnology”.

http://www.nano.gov/node/681 http://nanopatentsandinnovations.blogspot.com/2011/10/federal-government-releases.html

Nanotechnology Safety – in the EU

This Legislation is the first regulation ever to establish rules of use of engineered nanomaterials in products of any type

Regulation of the European Parliament and of the Council on Cosmetic Products, PE-CONS 3623/09 (2009)*

* Published online: http://register.consilium.europa.eu/pdf/en/09/st03/st03623.en09.pdf

Nanomaterial Sampling

Aerosol Inlet

Bukowiecki, N., Dommen, J., Prévôt, A.S.H., Richter, R., Weingartner, E., Baltensperger, U. 2002. A mobile pollutant measurement laboratory—measuring gas phase and aerosol ambient concentrations with high spatial and temporal resolution. Atmospheric Environment: 36(36-37): 5569–5579.

A Mobile Measurement Laboratory

Nanomaterial Sampling

Tsai, C.-J., Liu, C.-N.,Hung, S.-M., Chen, S.-C., Uang, S.-N., Cheng, Y.-S., Zhou, Y. 2012. Novel Active Personal Nanoparticle Sampler for the Exposure Assessment of Nanoparticles in Workplaces. Environmental Science and Technology: 46(8): 4546–4552.

A Personal Nanomaterial Sampler Collects both respirable PM (cutoff dae = 4µm) and nanopaprticles (cutoff dae = 100nm)

Mannequin Sampling

for Realistic Personal

Exposure Assessment

Nanomaterial Sampling

Nanomaterial Sampling

Thayera, D., Koehlerb, K. A., Marchesea, A., Volckens, J. 2011. Personal, Thermophoretic Sampler for Airborne Nanoparticles. Aerosol Science and Technology: 45: 734–740.

Thermophoretic Aerosol Sampler

Nanomaterial Sampling

http://www.grimm-aerosol.com

Electrostatic Nanoparticle Precipitator

Nanomaterial Analysis Techniques

Transmission Electron Microscopy

Scanning Electron Microscopy (SEM)

Energy Dispersive Spectroscopy (EDS)

Selected Area Electron Diffraction (SAED)

Aerosol Mass Spectrometry (AMS) for particle elemental analysis

Transmission and other kinds of Electron Microscopy can be used to study

nanoparticle size, shape, and agglomeration of nanomaterials including those

collected from ambient air in industrial and home spaces as well as outdoors

Methodology of Nanomaterial Analysis

Image from: http://www.virginia.edu/ms/images/JEOL2010.jpg Image from: http://nobelprize.org/educational_games/physics/microscopes/tem/index.html

Challenges when analyzing nanomaterials:

- Low electron-contrast particles (many organic and light-element materials) are invisible!

- Radiolysis – alteration of physico-chemical nature of certain material/particles by the

energetic electron beam.

Spatial or three-dimensional configuration of the particles and agglomerates

SEM Other Potential Measurement Techniques II

http://www.purdue.edu/rem/rs/sem.htm http://cermetmaterials.com/7558.html

Scan

nin

g El

ectr

on

Mic

rosc

op

y

Atomic composition of individual particles;

Elemental mapping of particles

EDS Other Potential Measurement Techniques III

http://www.aspexcorp.com/Solutions/OmegaMaxtrade/EDXSpectroscopy.aspx

Ener

gy D

isp

ersi

ve S

pe

ctro

sco

py

Crystalline structure of particles;

Allows identification of:

• Certain chemical compounds and/or mineral types (crystal structures) of the same compounds, e.g. rutile or anatase forms of titanium dioxide (TiO2)

SAED Other Potential Measurement Techniques IV

http://www.slh.wisc.edu/wohl/wohlworks/analysis_inorganic/36.dot http://www.nrel.gov/pv/measurements/transmission_microscopy.html

Sele

cted

Are

a El

ectr

on

Dif

frac

tio

n

Other Potential Measurement Techniques V

Near real-time chemical analysis of aerosol particles simultaneously with their size characterization;

Chemical identities of individual aerosol particles can be determined

AMS

http://cires.colorado.edu/~jjose/amsanimation.gif http://ahorrey.com/?action-viewnews-itemid-35848

Aer

oso

l Mas

s Sp

ect

rom

etry

Example Results of TEM Analysis

Sample 1

Sample 2

Aerosol Measurement Techniques

High importance of nanomaterials in all size fractions (both 1 – 100 nm and above in the agglomerated form) → we need to use more than one measurement technique, e.g. SMPS and APS

http://www.tsi.com/ProductView.aspx?id=21939 http://www.tsi.com/ProductView.aspx?id=23007

Example Results of SMPS, APS Analysis

Wide particle size distributions in the aerosol (airborne phase)

Sample 2 Sample 1

Primary Nanoparticle Size ≠ Aerosol Particle Size

In aerosol, nanomaterials are likely distributed in particles across a particle size range extending beyond 1 – 100 nm up to supercoarse particles (10 – 20 µm)

Challenges of Combined Use of Several Aerosol Measurement Techniques

SMPS measurements are based on the electrical properties of particles

APS measurements are based on the aerodynamic properties of particles

The different detection principles can result in different detection efficiency

This effect is often seen in the transition size range (0.5–0.7 µm) depending on various aerosol characteristics

TSI offers Merge Software to combine SMPS and APS measurements

A range of particle parameters including density and shape factor are required

Presenting the data as is – is an option: unaltered SMPS and APS size distributions

Challenges of Combined Use of Several Aerosol Measurement Techniques

Diverse range of particle materials and types in the aerosols derived from consumer products

Requires

?

Conclusions Nanoparticles are ubiquitous indoors and outdoors and include

engineered as well as incidental ultrafine particles, e.g., from combustion

sources;

Exposure to ultrafine including engineered nanoparticles causes adverse

health effects;

Regulation of nanomaterials will greatly expand;

Existing sampling and analytical techniques do allow collection and

characterization of ultrafine particles including engineered nanomaterial

particles;

The particle size distributions are different in: (1) the original nanomaterial

preparation, (2) a nanotechnology-based product that incorporates

nanomaterial(s), and (3) the derived aerosol causing exposure;

At this point, especially for the ambient ultrafine aerosols, it is a challenge

for the existing analytical techniques to identify certain nanoparticles or

distinguish between engineered nanoparticles and incidental ultrafine

particles.

Questions?