detecting, handling and controlling nanoparticle ......detecting, handling and controlling...

Final Report for WorkSafeBC and Workersrsquo Compensation Board of Nova Scotia

1

Detecting Handling and Controlling

Nanoparticle Contamination in the Workplace

Byron D Gates Francesco P Orfino James H-W Zhou Michael TY Paul Amir Nazemi Yasong Li

Department of Chemistry and 4D LABS Simon Fraser University 8888 University Drive

Burnaby BC V5A 1S6 Canada

Principle Investigator to whom correspondence should be addressed Email bgatessfuca

Tel (+1) 778-782-8066 Fax (+1) 778-782-3765

Project number RS2010-IG40

Submission date of final report June 7 2013

Acknowledgements This research was supported in part by WorkSafeBC (Workers

Compensation Board of British Columbia) and the Workersrsquo Compensation Board of Nova

Scotia through the FOCUS ON TOMORROW program the Natural Sciences and

Engineering Research Council (NSERC) of Canada through a Discovery Grant and the

Canada Research Chairs Program (BD Gates) This work made use of 4D LABS shared

facilities supported by the Canada Foundation for Innovation (CFI) British Columbia

Knowledge Development Fund (BCKDF) Western Economic Diversification Canada and

Simon Fraser University We also thank Cindy Collins and the Canadian Olympus Innov-X

team for on-going support of this research project through in-kind contributions of their time

and equipment


2

TABLE OF CONTENTS

POINT FORM SUMMARY 3

EXECUTIVE SUMMARY 4-5

MAIN REPORT 6-29

i METHODOLOGY 10-15

ii PROJECT FINDINGSOUTCOMES 15-23

iii IMPLICATIONS FOR FUTURE OCCUPATIONAL HEALTH RESEARCH 23-24

iv APPLICATIONS FOR POLICY AND PREVENTION 24-28

v KNOWLEDGE TRANSLATION AND EXCHANGE 28-29

REFERENCES 30-33

FIGURES AND TABLES 34-44


3

POINT FORM SUMMARY

1 We have investigated the remediation of nanoparticles in the workplace environment focused on

exposure resulting from the accidental spill of a solution containing the nanomaterials The small size of

these materials prevents us from seeing these particles with an unaided human eye The hypothesis is

that spills containing nanoparticles would therefore go unnoticed in the workplace

2 We have reviewed the analytical techniques that could be used for identifying the presence and extent

of unnatural nanoparticles in the workplace which are seen as contaminants (ie potentially harmful to

the workers) Our goal was to identify a method or methods that are suitable to be widely implemented

in the workplace at the source of the potential contamination but without a significant cost for

implementation and analysis

3 We have also evaluated various techniques for controlling spills containing nanoparticles by

encapsulation Control was primarily sought through encapsulation of the nanoparticles to prevent

spreading of the contaminant through either physical contact or formation of an aerosol We have also

focused on simulating spills of nanoparticles on workplace countertops as this would be one of the most

likely places to encounter a spill

4 We have also assessed our ability to clean-up spills containing nanoparticles This investigation

utilizes the techniques identified (as per the tasks outlined above) for use in the workplace to assess the

remediation of the nanoparticle spills We assessed the remediation of various types of nanoparticles to

understand the potential limitations of remediating various forms of contamination

IMPLICATIONS FOR POLICY AND PREVENTION

1 Workers using nanoparticles should be aware that potential spills containing nanoparticles can easily

go unseen by the unaided human eye Our simulated spills of nanoparticles on workplace countertops

were not clearly distinguishable from a clean countertop but could be identified using the appropriate

technique(s) Potential spills could remain unattended and could lead to further spreading of the

nanoparticle contaminant throughout the workplace

2 A number of techniques could be used to identify the presence of nanoparticle contaminants in the

workplace A number of these analytical techniques are being used on a regular basis to characterize

nanoparticles and could be implemented as methods to monitor spills containing nanoparticles A

question that must be answered by the larger community is how much information is required to identify

the need for remediation Prior knowledge of what nanoscale materials are being used in the workplace

and specifically when and where these materials are being used provide key information for quickly

assessing the need for nanoparticle remediation

3 Containment of nanoparticle spills is an effective means of controlling a spill containing

nanoparticles to minimize the potential for spreading to other surfaces in the workplace Some methods

of containment can efficiently communicate to other workers the presence and extent of contamination

The means of containment can also provide an efficient means for remediation of the nanoparticles

Further work is necessary to develop methods and materials specifically for remediation of

nanoparticles and may need to be customized to the type of nanoparticle being remediated and based its

interactions with the contaminated surface(s)

4 It is possible to remediate nanoparticle spills and to follow the remediation process with a number of

analytical techniques We implement some methods of remediation and detection as a demonstration

and show that these tools can be used to train workers on appropriate (and inappropriate) methods of

remediating nanoparticle spills This education on spill clean-up will be very helpful to train workers on

best practices in the workplace but further decisions must be made regarding what extent of

decontamination is necessary for the workplace Further work is necessary to correlate the presence of

particular nanoparticle spills to their potential health concerns (from both acute and prolonged

exposures)


4

EXECUTIVE SUMMARY

The small size of nanoparticles ndash one nanometer is one-billionth the length of a meter ndash opens the door

to a number of potential applications for these materials based on their small size and their associated

(and sometimes unique) properties The small size of an individual particle prevents us from observing

it by human eye without the use of specialized techniques A wide range of specialized techniques have

been established for aiding the investigation into the dimensions shapes and other properties of

nanoscale materials These techniques include scanning and transmission electron microscopies atomic

force microscopy and adaptations of optical microscopy methods These techniques offer workers an

ability to characterize individual nanoparticles studies that are important to learn the properties of these

materials Aside from the use of these specialized techniques we can sometimes easily see larger (eg

milligram) quantities of these particles when concentrated into a powder However when these

materials are dispersed into a solution or spread onto the surfaces of a material it can be impossible for

us to discern the presence of nanoparticles Considering the small size of these particles how can a

worker identify a potential spill of nanoparticles in the workplace What tools can aid the worker in

identifying the presence of a spill and the extent of the spill If a spill was identified how would the

worker communicate that to other workers and also contain the spill Is it possible to remediate the spill

of nanoparticles in a cost-effective and timely manner What techniques are best suited for remediation

of these types of spills

It is highly likely that spills containing nanoparticles in the workplace could be predominately found on

the countertops of a laboratory the place where workers are most likely to dispense mix and otherwise

manipulate solutions containing nanoparticles Techniques for identifying the presence of these spills

must be brought into the workplace Many analytical techniques that are specific to identifying the

presence of a nanoscale material require specialized infrastructure to operate which excludes their

ability to be easily transported to any workplace In addition sample preparation required by some

analytical techniques is rather extensive requiring a significant time investment We sought an

analytical technique that is both portable (ie can be brought into the workplace to the point of the

potential hazard or contamination) and requiring little to no sample preparation The goal was to

identify a technique that could enable rapid feedback to the worker on the presence of and extent of a

potential spill In most cases the knowledge of the worker handling the nanoparticles can also be

utilized to assist in the identification and remediation of a potential spill These workers know what

nanoparticles they were using in the workplace as well as where they were handling these materials

We identified x-ray fluorescence spectroscopy as a portable solution to potentially identify the presence

and extent of a spill containing nanoparticles Many other techniques could also be utilized but the ease

of use at the point of contamination without the requirement of sample preparation makes this an

attractive solution in nanoparticle remediation

A spill could become a larger concern if the spill is not contained Contaminants can spread by physical

contact with a liquid containing the nanoparticles or solid contact with the nanoparticles Particles could

transfer to gloves clothing skin or supplies in the workplace which become secondary sources of

contamination and further spread the particles throughout the workplace It is also possible that the

particles within a spill could form an aerosol and spread to even more surfaces This form of transfer

does however depend on the type of interactions between the particle and the contaminated surfaces

(eg countertop) and the presence of mechanisms to assist in aerosol formation The presence of and

extent of aerosolized nanoparticle contaminates is beyond the scope of the current studies We still

however evaluated a range of techniques that could encapsulate nanoparticle contaminates We sought

a solution that would contain the nanoparticles and if necessary communicate to other workers the

presence of these unseen contaminants We did not identify one universal technique for encapsulating

nanoparticles but using the knowledge learned in these studies a solution could be purpose-built for


5

indicating the presence of a contaminant encapsulating that contaminant and assisting in its removal

from the workplace

Remediation of nanoparticles spilled in the workplace requires a method of acknowledging that these

unseen particles are appropriately being removed and to avoid spreading these particles to a wider

extent throughout the workplace We combined the use of analytical techniques to monitor the presence

of nanoparticle contaminants and encapsulation techniques to assess the appropriateness of a series of

techniques for remediation of these spills We were able to demonstrate an ability to progressively

remove nanoparticle contamination Some methods were more efficient than others but the success of

the methods evaluated in these studies depended on the type of nanomaterial (eg size and shape) and

its interactions with the contaminated surfaces These studies indicated that further work is necessary

each remediation technique must be evaluated in context of the type of nanoparticle being cleaned up

and the surfaces it is in contact with For example a smooth or otherwise polished countertop presents a

different challenge for remediation than a rough or semi-porous countertop Further work is required to

develop a larger working knowledge of remediating nanoparticles in the workplace We also

demonstrate the need for proper training of workers on methods of clean-up in order to not overlook a

spill andor to spread the spill over a larger area

Methods for remediation of nanoparticle contaminants need to be simple easy to implement efficient

and effective Remediation may be pursued either through work training or through a third party

contracted to clean-up a work environment The same third party could be contracted for assessment of

the workplace environment for potential contaminants as an assessment of the health impacts of the site

Whatever the approach to detection assessment and remediation of the workplace from nanoparticle

contaminants further work is also necessary to determine the potential acute and long-term health

impacts of nanoparticles in the workplace

There remain many unanswered questions in dealing with nanoparticle contamination What level of

contamination is acceptable How do the levels of contamination in a common workplace rather than

the simulated environments here correspond to health concerns of the worker What types of materials

are of the highest concern for remediation Presumably there should be a correlation to the reactivity of

a material in the ambient environment andor with a worker that might come into contact with the

material How often should a workplace be inspected for potential contamination This will likely

correlate with the particular habits of a workplace such as how often how much and what types of

nanoparticles are used by workers To answer these important questions further analysis is required

from a broad spectrum of investigators It would be most efficient to build a larger team of scientists to

collect data to address some of these questions The outcome of these investigations and the

implementation of policies in surrounding nanoparticle contamination in the workplace should be driven

by data Too many questions remain to draw a conclusion at this time on the importance or not of

nanoparticle contamination in the workplace However in the exclusion of sufficient data it is prudent

to avoid or otherwise minimize a workerrsquos exposure to nanoparticles

In summary the findings of these studies suggest that simple methods can be implemented to contain

and remediate nanoparticle contaminants from the workplace Simple techniques can also be

implemented to communicate the presence of nanoparticle contaminants A number of analytical

techniques could be used to determine the presence of nanoparticle contaminants but the technique(s)

should be chosen according to the needs of the remediation effort Further work is required to establish

appropriate techniques for implementation in the workplace but a foundation has been laid that

demonstrates the importance of worker training for proper methods of handling nanoparticles and

cleaning up potential spills

Keywords nanoparticles workplace safety contamination spill remediation


6

MAIN REPORT

The potential hazards associated with exposure to nanoparticle contamination in the workplace is of

widespread concern considering the large numbers of nanoparticles being produced and used in work

areas around the world Nanoparticles have become as commonplace as many other types of materials

in the modern laboratory[1-3]

The chance for spilling is no less than for spilling any other material

handled in the work environment The concern in the case of nanoparticles is the unknown A spill of

greater than 1 billion particles may easily go unnoticed by the unaided human eye Workers that contact

this spill may accidentally transfer particles to other parts of the workplace thus the contamination may

spread to more than just a laboratory bench This unseen spill may persist in the workplace

environment leading to either acute or prolonged exposure to the nanomaterials In order to address the

potential for an acute exposure one needs to understand the concentrations of particles that could

contaminate the workplace and go unseen In addition an acute exposure depends upon the specific

particle its interaction with the environment and its potential interaction with a worker The potential

for a prolonged exposure of a worker to a spill of nanoparticles also requires an intimate knowledge of

how these nanoparticles interact with their environment and a human being[4-7]

The biotoxicity and

ecotoxicity are beyond the scope of this current study but are included in ongoing studies throughout

the world[8-13]

In the studies reported here we aim to develop a better understanding of the types of

spills that may be encountered in the work environment the level of nanoparticles that might be

encountered and yet unseen as well as methods to detect and remediate this contamination from the

workplace

If a spill of nanoparticles is unseen by the human eye how can it be expected that the workplace

environment be properly assessed for potential contamination There are a number of analytical

techniques that are already being pursued to characterize nanoparticles that are both naturally formed

and synthetically produced These same techniques could be and in some cases are utilized to

diagnose nanoparticles in our environment such as carbon-based nanostructures which are found in


7

exhaust pollutants from the combustion of petroleum based products[14]

A sea breeze also contains

nanoparticles but in the form of various salt crystals and silica particles[15]

Nanomaterials are also

being characterized in products that you can buy off-the-shelf[16-18]

such as silver laden socks that act as

antimicrobial agents[1920]

The techniques to characterize these particles are very diverse and can

provide detailed information of size composition shape and even atomic defects within the material

The criteria used to select the best analytical technique to fully characterize a nanoparticle are however

different from the criteria used to determine which of these techniques are most appropriate for use in

the remediation of nanoparticle contamination

Identifying the presence of a nanoparticle contaminant in the workplace could potentially require the

assessment of a relatively large number of surfaces in order to account for primary spills and secondary

transfer of material to other surfaces Multiple areas within the workplace would have to be tested since

it is not easy to identify the presence of nanoparticles The amount of time required to prepare these

samples for analysis and to analyze the samples could be overwhelming For instance consider the case

where 1000 independent measurements are taken within the workplace Some techniques require

acquiring a sample packaging and labeling of the sample work-up and analysis and identification of

the results with the specific location in the workplace It may require ~30 min to carry out these tasks

for one sample This would translate into ~12 weeks to obtain the final analysis A significant amount

of time is invested in obtaining packaging tracking preparing and analyzing the sample It is

preferable to analyze the sample at its point of origin and avoid the need to obtain package and track

the sample In addition it would be desirable to minimize or avoid any need for sample preparation

such as acid digestion of the sample A portable technology could be brought to the site of potential

contamination but the technique should still provide analytical information on the presence of

nanoparticles

Information about the nanoparticles could be utilized to simplify the task of discerning the presence

of a contaminant The workers will often know some information about the materials they are handling


8

such as the composition average size and possibly shape of these materials Size and shape of the

nanoparticle are not essential pieces of information if the composition of the nanoparticle is foreign to

(unique in) the workplace environment There are a number of techniques that can quantitatively

analyze a sample for its elemental composition A number of these analytical techniques are identified

in Table 1 each capable of analyzing samples for a wide range of elements[21-23]

A large variation is

observed in the amount of time required for analysis (including sample preparation) and for the cost of

procuring equipment associated with each technique The limit of detection also significantly varies

between these techniques The concentration of nanoparticles per area deemed to be safe in the

workplace is beyond the scope of this study and will require further analysis However based on the

typical concentrations of nanoparticles in solution our initial calculations suggest that the ideal method

of analyzing nanoparticles in the workplace should at least detect concentrations as low as parts per

million (ppm) levels This estimate is supported by our studies to simulate spills of solutions containing

nanoparticles Keeping in mind each of the considerations outlined above the top two techniques are

laser induced breakdown spectroscopy (LIBS) and x-ray fluorescence spectroscopy (XRF) These

techniques are each relatively inexpensive portable sensitive to ppm levels without the need for sample

preparation and offer relatively fast sample analysis Analysis by LIBS can be locally destructive to

~100 nm of the surfaces under analysis but is considered a non-destructive technique as this damage

might not be discernable by eye[24]

We identified XRF as the desired system to pursue for these initial

studies but other analytical techniques such as LIBS might be of interest for future studies in the area of

assessing nanoparticle contamination

X-ray fluorescence spectroscopy is an ideal method for analyzing multiple samples throughout the

workplace[25-27]

There are a number of commercially available portable XRF systems that are designed

to be brought ldquointo the fieldrdquo for analyzing samples on site[27-29]

These developments have lead to a

number of advantages for using XRF technology to track nanoparticle contamination The portable

XRF technologies are manufactured with the knowledge that users may want to collect information on


9

the samples that include time date sample number and location All of this information can be

automatically logged by the system using an on-board data logger with an integrated global positioning

system These systems are not essential for our studies but for the proposed hypothetical analysis of

1000 independent samples these capabilities would significantly reduce the time required to inspect a

workplace for contamination If each sample required 3 min to complete the analysis and logging of the

data it would still require ~1 week of analysis Although this is a ~12x improvement in throughput it is

clear that the analysis of nanoparticle contamination does require a relatively simple quick and yet

informative analytical technique Analysis by XRF could be easily implemented on a regular basis by a

worker or on an occasional basis by a third party The regularity of inspection will be determined in

part by the frequency with which the nanoparticles are used in a particular workplace

An essential aspect of remediation will be the method by which a spill of nanoparticles is cleaned up

and how the presence of these contaminants is communicated to other workers Remediation of a

contaminant requires removal of the contaminant from the environment of concern Determining the

success of a remediation process can however be difficult to discern A contaminant that is spread

over a larger area is still present but might no longer be detectable One approach might be to train

individuals on appropriate methods of remediation However considering that unintentional contact

might result in the spread of a nanoparticle contaminant it is equally important to establish a set of

methods that can remediate nanoparticle contaminants while minimizing physical contact between the

worker and the potentially hazardous particles A method of wiping or otherwise washing the

contaminated surfaces could displace the nanoparticles but may also spread the nanoparticles to other

surfaces (eg wash cloth sponge or other material used to wash the surfaces) Our initial studies

reported herein demonstrate how traditional methods of cleaning up a spill can lead to further spreading

of the contaminants to other areas of the laboratory Nanoparticles can be dissolved through acid

digestion but this would present obvious challenges for use as a decontamination technique in the

workplace The method we introduce here is to remediate the nanoparticles by a process of


10

encapsulation We pursue a number of different methods of encapsulation that could be adapted to

many different types of surfaces found throughout the workplace The encapsulation process provides a

simple means to contain the nanoparticles and minimize andor prevent further contact between the

worker and the contaminant Although some encapsulating layers might remain in place our aim was to

completely remove the potentially hazardous material from the workplace and to not physically or

chemically alter the countertops and other surfaces in the workplace A secondary feature of the

encapsulation process is that the encapsulating material could be color coded to indicate to other

workers the potential presence of contamination by nanoparticles We have identified methods that can

encapsulate the nanoparticles communicate the presence of these contaminants and effectively remove

the particles when the encapsulating layer is peeled away from the contacting surfaces

Further work will be necessary in the field of nanoparticle contamination in the workplace The

outlook could include further development of better materials and methods to encapsulate or otherwise

bind the nanoparticles as well as optimizing the use of analytical instrumentation (eg XRF LIBS) for

the detection of nanoparticles The on-going studies will however require further collaboration to

establish the potential health impact of nanoparticle contaminants on surfaces found in the workplace

This work will include determining the potential correlations between level of contamination type of

contamination duration of exposure and the immediate and long-term health of a worker We are

however pursuing outreach activities to promote further discussion discovery and development in this

field These activities and other aspects of future work are outlined herein

i METHODOLOGY

We focused on simulating the contamination of workplace countertops Other surfaces in the

laboratory could also become contaminated with nanoparticles but the primary route of contamination

is most likely from accidental spills when handling solutions of nanoparticles Future work may extend

this analysis to flooring materials glass windows in the workplace and glass sashes in fume hoods and

clothing materials that include laboratory coats Our focus was on the contamination of representative


11

samples of laboratory countertop coupons (~1 cm2) with solutions containing nanoparticles The

material evaluated in this study is a black Wilsonart D417-335-01 countertop used in many of the

laboratories at Simon Fraser University All countertops used in this study were from uninstalled

sections of countertop cut into ~1 cm2 pieces for the purposes of simulating contamination by

nanoparticles thus sections of countertops installed in the laboratory were not used in these studies

To simulate contamination from a spill of nanoparticles we prepared aqueous solutions of gold

nanorods Gold nanoparticles were one of the chosen simulated sources of contamination because they

are one of the most widely studied nanoparticles[30-33]

To prepare the gold nanorods[34]

we first

prepared an aqueous seed solution of 05 mM HAuCl4 (5 mL) 02 M cetyl trimethylammonium bromide

(or CTAB) (5 mL) and 10 mM cold NaBH4 (600 microL) A separate solution was prepared by mixing 1

mM HAuCl4 (10 mL) 02 M CTAB (10 mL) 4 mM AgNO3 (500 microL) and 788 mM ascorbic acid (140

microL) Once the latter solution became transparent we added 24 microL of the seed solution to the growth

solution and maintained the solution temperature at 37oC for 3 h The resulting solution had a faint red

coloration We centrifuged this solution for 20 min at 8500 rpm decanted the supernatant and replaced

it with high purity water This purification process was repeated two more times to remove excess

reagents and CTAB from the gold nanorod product The product of ~38 nm long and ~11 nm wide gold

nanorods was verified by transmission electron microscopy (TEM) analysis using either an FEI Tecnai

G2 F20 scanning TEM (STEM) with a field emission gun thermionic source operating at 200 kV or a

Hitachi 8000 STEM with a lanthanum hexaboride thermionic source operating at 200 kV For this

analysis samples were prepared by drop-casting or dip-coating solutions of nanoparticles onto a 300

mesh copper grid coated with formvarcarbon (catalogue number FCF300-CU-50 Cedarlane Labs)

We also have extensive experience manipulating the surface chemistry of gold nanoparticles[35-37]

The modification of their surfaces was important for tracking these nanoparticles We tagged the

surfaces of the nanoparticles with a fluorescently molecule This tag consisted of a long-chain

poly(ethylene glycol) (or PEG) terminated on one end with Rhodamine B and on the other end with a


12

thiol that would bind to the gold surfaces[38]

We prepared these HS-PEG5000-NH-Rhodamine B

molecules by reacting 42 mg HS-PEG5000-NH2 with 9 mg of Rhodamine B-isothiocyanate dissolved in

500microL of DMSO and 10 microL of NN-diisopropylethylamine This reaction mixture was stirred for 3 h at

room temperature and purified by dialysis with high purity water (182 MΩcm water purified using a

Barnstead Nanopure DIamond Life Science water filtration system) A solution of the HS-PEG5000-NH-

Rhodamine B was mixed with the CTAB coated gold nanorods at room temperature for a period of 2

days but stored in the dark to minimize exposure to ambient light The mixture was purified by size

exclusion chromatography using a column containing Sephadex G-25 gel[38]

Elution with water and

pressurized air removed unreacted CTAB coated gold nanorods and the unbound HS-PEG5000-NH-

Rhodamine B Subsequent elution with PBS buffer (pH 74) yielded the desired product of gold

nanorods tagged the Rhodamine dye (or GNR-S-PEG5000-NH-Rhodamine B)

The number of gold nanorods in solution was quantified by a combination of extinction spectroscopy

and inductively coupled plasma optical emission spectroscopy (ICP-OES) techniques[39]

A typical

solution had an optical density (OD) at 754 nm of 171 corresponding to ~23 times1014

gold nanorodsL

solution We believe this concentration of nanoparticles is representative of solutions that would be

typically used in many other laboratories Simulated spills on the Wilsonart countertop coupons were

prepared by drop casting 2microL of solution containing the suspension of GNR-S-PEG5000-NH-Rhodamine

B This simulated spill of nanoparticles is difficult to discern by eye unassisted but through the use of

a fluorescence microscope we can easily track the spill A Zeiss Axio M1m Microscope equipped with

a filtered HBO 100 mercury lamp was used to excite the Rhodamine B (filter set purchased from

Chroma Technology 41002 - TRITC (Rhodamine)DiICy3trade) Fluorescence images at 50x or 500x

optical magnification were captured with a Zeiss AxioCam MRc5 Camera and fluorescence spectra

from the samples collected using a Princeton Instrument Acton spectrometer equipped with a PIXIS 400

CCD detector cooled to ndash72degC Fluorescence spectra were acquired from 300 to 700 nm using Winspec


13

32 software a shutter speed of 100 ms and a slit width of 205 microm Spectral position of the fluorescence

spectra were calibrated using the emission lines of the HBO mercury lamp

Remediation of the simulated contamination from gold nanorods was pursued through both a

traditional method of wiping and separately by a method of encapsulation The first method consisted

of using a paper towel wet with water and either wiping the spill in a linear or circular fashion The

method of encapsulation used an off-the-shelf product liquid polymer solution (New-Skin Liquid

Bandage) The polymer solution was cast onto the contaminated surface and the solvent evaporated

thoroughly before the polymer film was peeled away from the samples of countertop material We

determined that the best method for peeling these polymer films from the rough countertop surfaces was

to use a framework made from adhesive tape which provided support to keep the flexible polymer film

from pulling apart

A second method of encapsulating the nanoparticle contaminants was pursued using adhesive tape as

another off-the-shelf product for remediation For these studies polished silicon wafers were cut into

~1 cm2 pieces and cleaned with a Piranha solution and rinse with 182 MΩcm water The Piranha

solution was prepared from a 72 (vv) mixture of concentrated sulfuric acid and a 30 by volume

aqueous solution of hydrogen peroxide The polished silicon pieces were soaked in Piranha for 15 min

and rinsed at least three times with ~50 mL of 182 MΩcm water deionized water CAUTION Piranha

solution is a strong oxidizing agent and reacts violently with organic compounds This solution should

be handled with extreme care The countertop was cut into ~1 cm2 pieces and cleaned with a 5 nitric

acid solution and rinsed three times with ~50 mL high purity water CAUTION nitric acid is a strong

oxidizing agent and reacts violently with many compounds This acid should be handled with extreme

care The contaminant for the evaluation of adhesive tape remediation was silver nanoparticles which

are also widely used in research studies and have been introduced into some consumer products[1920]

These particles were prepared according to a literature preparation[40]

by dissolving 50 mg silver acetate

in 1901 mL octadecene in a 250 mL round bottom flask When the silver acetate was completely


14

dissolved 615 mL oleyamine was added to the flask This flask was heated to 175degC in a silicone oil

bath for 15 min and immediately transferred to another silicone oil bath pre-heated to 180degC After

heating for 1 h the flask was cooled to room temperature and divided into falcon tubes and mixed with

chloroform at a 11 (vv) ratio Silver nanoparticles precipitated from solution after addition methanol

in a volume equivalent to that of the chloroform This mixture was centrifuged at 8500 rpm for 25 min

the supernatant decanted and precipitate dispersed into methanol This process of purification was

repeated two more times and the purified silver nanoparticles dispersed into hexane A simulated spill

was prepared by drop casting 10 L of solution containing the nanoparticles onto the pieces of either

polished silicon or countertop and dried for gt30 min A piece of 3M Scotchreg Magic adhesive tape

(~15 cm in length and 19 cm wide) was placed over the contaminated surfaces A plastic cylinder was

used to apply an even pressure across the surface to ensure uniform adhesion between the tape and these

surfaces The adhesive tape was removed by peeling along the length of the tape and the remediation

process repeated as necessary with a new piece of adhesive tape Samples were analyzed at regular

intervals such as after 1 5 10 and 15 times remediation Elemental analysis was performed using a

Horiba Jobin-Yvon Ultima II ICP-OES or either a portable Delta or X-5000 XRF system from Olympus

Innov-X Samples were prepared for ICP analysis by digestion in 5 mL of 255 nitric acid and the

OES was monitored at an emission of 338289 nm The XRF analyses were performed using a tantalum

anode x-ray tube with a triple beam method and scan times of 45 s per sample

A third method of remediation by encapsulation of the nanoparticle contamination was pursued using

a synthetic rubber For this analysis we pursued another type of contaminant We prepared selenium

nanowires to simulate the remediation of a semiconducting nanomaterial and an element that is common

to many types of quantum dots and nanoparticles pursued in the literature and commercially available as

contrast agents for biological imaging or in solar cells[41-44]

To prepare the selenium nanostructures we

dissolved 273 g of selenious acid in 100 mL of 182 MΩcm water within a 250 mL round-bottom flask

and cooled this solution in an ice-water bath[45-47]

We added 3 mL of hydrazine (50-60 in water) to


15

the selenious acid solution We added the reducing agent in a drop-wise manner over a 2 min period

under continuous magnetic stirring After 15 min we collected the red precipitate by filtration The

filtrate was rinsed with ~200 mL ice-cold high purity water to remove residual hydrazine The isolated

red solid was stored in a desiccator while protected from exposure to ambient light Selenium

nanowires were prepared by subsequently sonicating for 1 min a dispersion of 1 mg red solid

(amorphous selenium colloids) in 1 mL ethanol This solution was stored in darkness over a period of

gt12 h and the resulting product of nanowires isolated by centrifugation at 1500 rpm for 15 min The

supernatant was decanted and replaced with hexane A 10 L droplet of this solution was cast onto the

test surfaces to simulate a spill In this case the test substrate was a Canadian 1cent coin that was cleaned

by sonicating in water for 30 min briefly immersed in a bath of hydrochloric acid and rinsed with high

purity water The synthetic rubber used to evaluate the encapsulation of this simulated spill of selenium

nanowires was a commercial product Plasti-dip The solution was vigorously shaken and applied as a

thin coating sufficient to cover all exposed surfaces of the coin This coating was dried for 10 min

before adding a second top coat After an additional 30 min the rubber coating was gently removed

using handheld tweezers The samples were analyzed by scanning electron microscopy (SEM) images

and energy dispersion x-ray spectroscopy (EDS) This data was acquired with an FEI Strata DB235

field emission SEM operating at 5 kV Samples for SEM and EDS analysis were prepared by drop-

casting a solution of nanowires onto the coin and evaporating the solvent (eg ethanol) before further

analysis or encapsulation and remediation

ii PROJECT FINDINGS AND OUTCOMES

The most obvious approach to mediating a spill containing nanoparticles is to proceed by wiping the

surfaces with a cloth or paper towel This method of clean-up although effective for mopping up most

liquids might not be effective in completely picking up the contaminant However nanoparticle

contamination resulting from a spill of solids or from a solution whose solvent has evaporated could

adhere preferentially to the contaminated surfaces due to the increased interactions between these


16

materials Our initial investigation was to evaluate standard means of remediation as applied to spills of

nanoparticles A spill of these particles would be unseen by human eyes thus we added a fluorescent

molecule (Rhodamine B) to the surfaces of the gold nanoparticles through the use of a covalent linker [a

thiol modified poly(ethylene glycol) with a terminal amine] The fluorescent tag allows us to track the

position of these particles on various surfaces The particles prepared for these studies and described in

the previous section are referred to as GNR-S-PEG5000-NH-Rhodamine B The standard material to

evaluate contamination in our studies was a black countertop commonly found in laboratories at Simon

Fraser University Fluorescence associated with the nanoparticles was not easily observed by eye on

these black countertops but could be easily discerned through the use of fluorescence microscopy

(Figure 1a) We simulated a spill of nanoparticles by applying a 2 microL droplet of gold nanorods to

isolated pieces of countertop material Each droplet contained ~45x108 nanoparticles for an average

surface density of ~72x106 nanoparticlesmm

2 however the coffee ring pattern associated with the

residue of nanoparticles (Figure 1a) indicated a non-uniform distribution of particles Wiping the

sample with a linear motion spread the particles over the countertop as indicated by the increased

fluorescence signal in the region outside of the original droplet (Figure 1b) After a second wipe of the

countertop surfaces with a new paper towel we still observed fluorescence both inside and outside of

the spill (Figure 1c) A circular wipe of a separate spill did not improve the removal of the particles

(Figure 1d) Traditional methods of remediating these nanoparticles are more likely to spread the

contamination to a larger area than to remove the particles It is however difficult to quantify the

success of this or any other remediation process through the use of fluorescence images alone We used

fluorescence spectroscopy as a more quantitative method of identifying residual nanoparticles on the

countertop Fluorescence spectra associated with the original spill and the samples after wiping indicate

a significant decrease in the fluorescence of the sample (Figure 1e) but the signal intensity did not

decrease to the background values after repeated attempts to wipe-up the spill A method of wiping

away the residue from the spill could be created that does effectively remediate the nanoparticle


17

contamination This may however require significant training for others to properly implement the

cleaning method and workers could likely lapse into using the standard methods of wiping up a spill if

the procedures are too elaborate A simple and effective procedure is needed to clean-up a spill of

nanoparticles

We aim to develop a method of encapsulating the nanoparticle contamination Encapsulation would

ideally provide an effective barrier between the worker and the particles thus minimizing the potential

for transfer of the contamination to other surfaces The encapsulation would also provide a simple

means to remove the particles peeling the encapsulating layer away from contaminated surface would

ideally also remove the particles from these surfaces Our first approach to encapsulating the

nanoparticles within a spill was pursued by casting a polymer onto the contaminated surfaces Although

thin polymer films could be made readily available in the laboratory it is important that any worker has

access to the materials necessary for remediation We explored a simple solution through the use of an

off-the-shelf product for encapsulating the nanoparticles We cast a solution of liquid bandage onto the

spill The dried film formed a polymer layer that could be easily peeled away from the countertop This

film did encapsulate the fluorescently tagged gold nanoparticles (Figures 2a and 2b) but some of the

particles still remain attached to the countertop The technique for separating the polymer film from the

countertop was an important component of a successful remediation (Table 2) If the film was peeled

too quickly or if the physical stress on the film was too great the film would pull apart and might not be

easily removed from the countertop We also established the use of a polymer frame (eg adhesive

tape) to strengthen and provide support to the polymer film while it is being separated from these

surfaces Repeating this process of casting drying and peeling of the polymer film can remove more

nanoparticles from the countertop (Figure 2c) By the fourth process of remediation the nanoparticles

are removed to a level below the detection limits of the fluorescence spectrometer An alternative

method is required to verify the presence (or absence) of nanoparticles following this process X-ray

fluorescence and other methods of elemental analysis were pursued for the analysis of residual


18

contamination as will be discussed below We also explored alternative materials and methods for

encapsulating the nanoparticle contamination

Remediation by casting a polymer film onto a countertop establishes the technique of encapsulating

the nanoparticle contaminants and removal of these contaminants by separating the polymer from the

countertop There are however a number of limitations with this method that can be improved upon by

other methods of encapsulation These limitations include the technical difficulty in reproducibly

casting the polymer film such that the polymer has consistent properties For example the polymer

film can easily pull apart while peeling it away from the countertop if the material is too thin or the

polymer film is not consistent or if the method of peeling is too forceful (Table 2) Benefits of the

polymer film chosen for these studies were its ease of use compatibility with most surfaces and that it

was readily available (an off-the-shelf product) We kept in mind each of these benefits and limitations

when identifying alternative methods of encapsulation One alternative that we pursued was use of an

off-the-shelf adhesive tape which is readily available simple to use and a relatively robust material

The idea is that a worker would apply the adhesive tape to a simulated spill of nanoparticles (Figure 3)

After pressing the adhesive tape to create uniform contact with the contaminated surfaces the worker

would remove adhesive tape and any nanoparticles that adhere to this tape

We initially demonstrated nanoparticle remediation with adhesive tape by quantifying the

nanoparticles remaining on the surfaces with ICP-OES We established a model system of silver

nanoparticles deposited onto polished pieces of silicon wafer that had an area of ~1 cm2 A standard

amount of nanoparticles was deposited onto each piece of wafer and the solvent was allowed to

evaporate over a period of hours simulating a forgotten or overlooked spill The adhesive tape was

applied and pressed into contact with the surfaces After a period of contact with the contaminated

surfaces the adhesive tape would be peeled away from the surfaces One of our initial concerns was

that the adhesive tape would leave too much residue on the contaminated surfaces thus nanoparticle

remediation would not be effective A quantitative analysis by ICP-OES of the silver residue after the


19

first step of remediation (ie one time application and removal of the adhesive tape) demonstrated a

significant decrease in the amount of silver relative to the contaminated surfaces (Figure 4) The first

application of adhesive tape decreased the silver concentration by a factor of nine (9) times Subsequent

steps of remediation with adhesive tape were however less effective than this initial step In fact

complete remediation requires more than 10 applications of adhesive tape There are a number of

factors that may play a role in the effectiveness of this remediation process These include the

possibility that although the first step of remediation removes some silver nanoparticles the subsequent

steps are hindered due to residual adhesive left on the surfaces from the initial application of tape In

fact the preparatory treatments performed to clean the polished pieces of silicon could have increased

the interactions between these silicon surfaces and both the nanoparticles and the adhesive tape It

could also be attributed to a non-uniform contact between the adhesive tape and the surfaces which

arise from the method used to apply the tape or due to topography resulting from multiple layers of

nanoparticles These factors should be even more significant when applying the adhesive tape to

rougher surfaces such as to countertops This model system confirms that off-the-shelf adhesive tape

can be used in the remediation of nanoparticles contamination

We mentioned in the introduction to this report that it is desirable to identify and implement

analytical techniques that could be used for identifying the presence of nanoparticle contamination and

tracking its remediation Based on criteria that we put forth we identified portable XRF technology to

be well suited to the task We evaluated XRF technology for monitoring the remediation of silver

nanoparticles from pieces of countertop using an adhesive tape to encapsulate and remove these

contaminants It was not surprising that the adhesive tape could effectively remove nanoparticle

contaminants from the countertop but there are some noticeable differences in the results when

comparing to the results from remediation of the silicon wafers (Figure 5) The first step of remediation

using adhesive tape is not as effective on the countertop as it was on the piece of silicon wafer This

could be attributed in part to the surface roughness of the countertop The silver nanoparticles were


20

however remediated to background levels as detected by XRF on the pieces of countertop after four

consecutive steps of applying and removing the adhesive tape Further steps of remediation may be

necessary to remove trace quantities of silver but these are below the detection limit of the XRF system

used in these studies

It is interesting to note the larger error bars associated with the XRF data relative to that of the ICP-

OES data Multiple measurements were made in either case but for the XRF we noticed a large

variation within the same sample These variations might be attributed to local changes in

concentration the samples analyzed by ICP-OES were prepared by digesting an entire sample in acid

but the samples prepared on the countertop were measured by XRF without further need for acid

digestion The resulting XRF signal also depends on the potential for loss of signal due to scatter of the

incident excitation or resultant emission[48]

To help elucidate this variation in response within the same

sample we set up a test scenario with pristine and contaminated pieces of countertop These samples

were analyzed by XRF at four independent positions of rotation between the substrate and the XRF

system each piece of countertop was analyzed by XRF subsequently rotated 90 degrees and the

process repeated The measurements (Figure 6) portrayed a large variation in signal intensity with the

angle of rotation The variations is silver on the contaminated sample could be attributed in part to local

variations in concentration of nanoparticles due to the effects of solvent evaporation[49]

There is also a

large variation in the signal obtained from the pristine samples (before contamination) at various angles

of rotation These results suggest a correlation between the orientation of the substrate and the portable

XRF system We kept the samples level and maintained a uniform separation between the XRF system

and our samples throughout these studies which could have otherwise lead to further variations in the

signal intensities Scatter can still arise from the interaction of the excitation source and emitted signal

with the roughened surfaces of the countertop The countertop coupons had a large variation in features

heights We measured the vertical profiles of multiple locations on the countertop coupons by

profilometry and determined a variation in vertical features of gt20 m (Figure 7) This variation in


21

feature height provides further insight into the potential for non-uniform contact between the

countertops and the adhesive tape We sought to combine the successes of remediation using adhesive

tape and with those using polymer films In doing so we sought a third method of remediating

nanoparticle spills

In our search for a third remediation material to encapsulate the nanoparticle contaminants we

identified a number of criteria that we also wanted to include as desirable attributes in the potential

product First among our criteria was to identify a material that could be cast against surfaces of

varying roughness and yet retain its material integrity (ie not pull apart) upon release from these

surfaces (eg a stretchable material) A similar criterion was to find a material that could be used to

temporarily coat various surfaces and upon removal leave no observable residue The final set of

criteria was that the material should be easily obtainable but also has an easily distinguishable

coloration that can be used to indicate the presence of a spill being remediated For this third approach

to encapsulating a spill of nanoparticles we chose a synthetic rubber that could be cast or sprayed onto a

variety of surfaces The material of choice contained a bright orange pigment to clearly identify the

location of the spill a spill might be initially identified through the use of XRF technology and then

marked by coating with the synthetic rubber The synthetic rubber that we chose was an off-the-shelf

product commonly used to coat plastics metals and other materials The resulting rubber film can be

removed from these materials and will stretch during removal without pulling apart into smaller pieces

In order to more quantitatively identify track and assess the remediation of nanoparticle spills from a

rough surface we changed the substrate to a Canadian 1cent coin This substrate contained easily

identifiable features and topography and was conducive to further investigation by electron microscopy

The previous remediation method demonstrated the utility of XRF to identify the presence of a spill and

monitoring its remediation but for the purposes of this study we wanted to understand how well the

encapsulating material removed the contaminant relative to adhesive tape For the purposes of these


22

studies we monitored the presence of the contaminant using both scanning electron microscopy (SEM)

and x-ray energy dispersion spectroscopy (EDS)

A bright orange synthetic rubber was chosen as a third material for remediation of spills containing

nanoparticles The orange stands out in contrast to the black countertop used in the previous studies

(Figure 8) The rubber coating once cured is easily removed from the Canadian coin We pursued a

third type of contaminant for these studies Selenium nanowires were chosen to demonstrate the

remediation of a semiconductor and specifically a material containing a less electron dense element

Selenium is also commonly used in the preparation of solar cells and light emitting nanoparticles

quantum dots and nanowires[41-47]

This nanomaterial therefore contains an element that might be

common to a number of work environments A spill of selenium nanowires is easily observed by SEM

analysis (Figure 8c) but after one process of coating and removing the synthetic rubber the nanowires

are no longer observable (Figure 8d) A more quantitative analysis can be obtained through the use of

EDS A coin was coated with selenium nanowires remediated through the application of an adhesive

tape (as described above) and analyzed by EDS for elemental composition (Figure 9) Another sample

was similarly prepared and remediated through the use of the synthetic rubber Comparing the

elemental composition of both samples (Figure 9) we were able to determine that remediation by

casting one film of synthetic rubber was effective at remediating the nanowires to levels below the

detection limit of the spectrometer In contrast the use of the adhesive tape required multiple repeat

processes to remove the same amount of contaminants from the recesses of the Canadian coin The

synthetic rubber was effective in remediation of a spill of selenium nanowires from relatively rough

surfaces

Further work is necessary to develop methods and materials for the remediation of spills containing

nanoparticles Some promising encapsulation materials have been demonstrated in the studies presented

herein A variety of contaminants were also demonstrated but further work is necessary to extend it to

other contaminants and to other surfaces that may become contaminated in the workplace However


23

remediation by encapsulation of the spill has been demonstrated to be an effective means of clean-up

and XRF technology could be used to track unseen spills in the workplace It remains to be seen how

these methods would be adopted in the work environment and if they would be properly implemented

to be effective In addition further work is required to identify the potential correlation between various

types of nanoparticles their concentration within a spill and the health of workers from acute and

prolonged exposure to these contaminants

iii IMPLICATIONS FOR FUTURE RESEARCH ON OCCUPATIONAL HEALTH

Future research into the identification and management of nanoparticle-based contamination will

require extending the remediation techniques to other nanoscale materials and developing other

materials and techniques for use in the remediation process The variety of nanoscale materials used in

the workplace is vast Some nanoscale materials may require further adaptations of the remediation

techniques in order to be effective In addition the types of surfaces found in the workplace are also

very diverse We evaluated countertops as a common place of contamination throughout many

workplaces Other possible places for contamination may include laboratory coats and clothing

Knowing if your clothing or washable laboratory coat is contaminated with nanoparticles might be

important to know how to wash and handle these items Nanoparticles from wash cycles can enter into

the waste stream and end up in water treatment plants[5051]

Another common surface for contamination

might be the metal or glass parts of a fume hood Of equivalent concern might be the various plastic

metallic or ceramic surfaces of common equipment found in the workplace and utilized for a wide

variety of tasks (eg hotplates pipettors) Detecting the presence of nanoparticle contaminants on each

of these surfaces presents its own set of challenges The Olympus Innov-X x-ray fluorescence systems

used in these studies were the Delta handheld and X-5000 desktop systems Other XRF systems from

Olympus Innov-X or another manufacturer might perform differently in the analysis of surface

contamination by nanoparticles In addition to these further analyses it would be beneficial to continue


24

seeking alternatives to the encapsulating materials pursued in this study Further developments could

produce a material that is optimized for remediation of nanoparticles

Aside from developing and expanding into new materials and techniques focused on nanoparticle

remediation from surfaces in the workplace there is a need for further work to assess the ability of

workers to implement the detection and remediation process on a regular basis Simulated studies such

as this one are often different from hands-on experience in the workplace The fact that the workers

would be remediating a material that is unseen by the human eye could lead to a general lethargic

attitude towards the procedures After a while it is possible that the procedures would be given up all

together Appropriate training and simplicity of the procedures are each essential components to

creating a solution that would be picked up and maintained by workers The techniques do however

need to be evaluated for their ease of use in the workplace and tested under a variety of laboratory

conditions

Longer term studies are required to provide further context for the results of this work through joint

efforts with researchers working in the area of biotoxicity and ecotoxicity of nanoparticles It will be

important to understand the correlations between the concentrations of nanoparticles observed on

various surfaces to potential mechanisms of contact by the worker These studies will depend on the

type of nanoparticle its environment and interactions with the contaminated surfaces Our goal is to

continue to promote further work in the safe handling of nanoparticles develop new methods to identify

and remediate potential spills and interface with other researchers working to develop analytical

techniques for nanoparticles andor to assess the implications of nanoparticles on health and safety

Some of these plans include continuing the outreach work as outlined in section v (below)

iv APPLICATIONS FOR POLICY AND PREVENTION

The obvious applications of the findings described herein include the detection and remediation of

nanoparticle contaminants in the workplace as well as the training andor reinforcement of best


25

practices for clean-up of nanoparticle spills in the workplace Those who will benefit from the

knowledge learned from these studies include workers using nanoparticles occupational health and

safety workers and regulatory bodies in charge of decisions impacting workplace health and safety

A primary recipient of the knowledge learned through these studies are occupational health and

safety workers who represent the front-line of defense in promoting a safe and healthy work

environment and who may perform their own research in this field These individuals can inform

workers of the potential concerns regarding the use of nanoparticles in the workplace They can also

provide information on the techniques available to the worker for identifying the presence of

nanoparticle contaminants in the workplace and best practices for clean-up of spills containing

nanoparticles These techniques are not universally ready for dissemination as the results of the

techniques demonstrated herein may vary depending on the type of contamination and the type of

surfaces that are contaminated Occupational health and safety workers performing research in the area

of nanomaterials could however assist in performing initial studies into the current practices in the

workplace and assist in evaluating a more widespread implementation of techniques described herein

The best means of avoiding a potential health and safety concern to workers is through avoidance of

the potential hazard but when that potential contact is unavoidable then appropriate actions must be

taken to ensure the safety of the workers These actions could include educating the workers on the

potential hazards associated with nanoparticles and exposure to spills of nanoparticles The second

major recipient of the knowledge learned from the studies reported here on remediation of nanoparticle

contaminants are those workers using nanoparticles in the workplace

The results of our work that could have the most immediate implications to workers using

nanoparticles is assisting them in understanding the correlation between methods used to clean-up spills

and the actual remediation of those spills The method used to clean-up a spill of nanoparticles is of

particular importance to avoid contaminants being spread throughout the laboratory environment It is

also important that the workers learn to communicate the use of nanoparticles and potential spills to


26

other workers Further work is also needed to assess the potential biotoxicity and ecotoxicity of the

types of nanoparticles being used in the workplace Nanoparticles used in these studies are some that

have been widely used in other laboratories but there is a growing diversity of nanoparticles used in the

workplace[1-3]

An understanding needs to be established between the concentration of nanoparticles on

a surface in the workplace and the potential for acute and long-term exposure with the associated health

and safety concerns A key outcome in our mind is that there needs to be further interactions promoted

between the workers using nanoparticles those developing analytical techniques for nanoparticles and

those workers developing best practices in the workplace for handling and otherwise using

nanoparticles We have promoted initial interactions between these groups as outlined in section v (see

below) and plan to continue these activities on an annual basis

There are many potential regulatory implications of this work It is however clear that further work

is required to provide sufficient data to assist in future decisions on regulating nanoparticle

contamination in the workplace For example a large effort is being pursued worldwide to better

understand the health implications of exposure to nanoparticles and is primarily focused on exposure

through ingestion inhalation or contact with the skin The results reported herein focus on nanoparticle

contamination in the workplace and potential means to remediate this contamination Further work is

necessary at the interface between these fields However regulatory implications could include the

promotion of opportunities for the researchers in these fields to work together towards the common goal

of promoting workplace health and safety

Further implications for regulatory bodies include promoting inspection of a workplace when there is

a change of a tenant at the request of a worker or at set intervals Regulatory bodies could also enforce

laboratory inspections as a means of assessing workplace habits and to reinforce best practices for

remediation of nanoparticle contaminants (and many other trace contaminants for that matter) Habits

could be adopted that suggest that something which is out of sight (eg nanoparticles spilled onto a

countertop) are also out of onersquos mind or in other words an unseen contamination is not of concern


27

The techniques outlined in this report offer a relatively economical and simple means for analysis of

numerous locations throughout the workplace The analytical techniques such as XRF could be

brought into the workplace to assist in a real-time assessment by acquiring the data of the potential

presence of and extent of nanoparticle contamination in the workplace Monitoring of the workplace

could be performed at regular intervals There is however currently a limitation to detecting low

concentrations of nanoparticle contaminants using such portable techniques Determining the level of

nanoparticle contamination that is acceptable by health and safety standards will require further work

and should include knowledge of the types of surfaces that could become contaminated (eg porosity

roughness) The development of analytical techniques that are purpose-built for detecting the presence

of nanoparticle contaminants in the workplace should be done in partnership with manufacturers of

analytical equipment An example is the optimization of a portable XRF unit with appropriate

excitation energies and electronic gains for detecting and quantifying the presence of nanoparticle

contaminants on various workplace surfaces these tools are often preset at the factor and optimized for

bulk materials such as alloys and pure metals Equipment manufacturers are driven by the demands of

the market The implications for regulatory bodies could be to encourage companies to competitively

build and offer equipment optimized for this new market

Nanoparticle contamination could have economic implications on a worldwide scale extending to

many Canadian companies Nanoparticles are being produced studied and incorporated into a wide

range of products some of which are already on the market The techniques demonstrated here could

be implemented by trained workers or by hiring a third party trained with these skills The potential

financial implications for the health care system are beyond the assessment of this study and will

depend on the type and duration of exposure and type of nanoparticle Through these studies we have

sought to establish techniques that are relatively simple and inexpensive to implement for monitoring

measuring and remediating potential nanoparticle contaminants We hope this work serves as an


28

inspiration to further research in the area to seek answers to the outstanding questions raised by this and

related work in the field of nanoparticle contamination

v KNOWLEDGE TRANSLATION AND EXCHANGE

We have sought to widely disseminate our results and discuss the implications of this on-going

research with a broad audience Our attempts to bring this work to a larger audience included attending

the CARWH 2012 conference held in Vancouver BC to present our research results and more

recently presenting these research results at NanoLytica 2013 held on March 14 2013 at Simon Fraser

University in Burnaby BC The latter one-day symposium was hosted at SFU and co-organized by

Prof BD Gates in partnership with PerkinElmer Funding for this event was provided in part by

PerkinElmer NSERC the Department of Chemistry at SFU and 4D LABS at SFU The event offered

free attendance to around 160 guests (including catered coffee breaks lunches and poster session) The

guests learned the research and development efforts taking place at the intersection of nanotechnology

and the analytical sciences The one-day symposium covered the development of new analytical

techniques for nanomaterials and the use of nanoparticles to develop new analytical techniques in areas

that included biomedical solar cells fuel cells and advanced materials and in an equally diverse set of

fields (eg life sciences materials sciences energy and the environment) The talks posters and meals

served as nucleation points for the attendees to engage each other in discussion on the topics being

presented This symposium presented an opportunity for attendees to interact with others from

government academic and industrial sectors Attendees learned of our on-going work in developing

methods to detect handle and otherwise control nanoparticle contamination and the future directions

that we are taking for this research This symposium offered an ideal forum to present our work to those

interested in developing analytical techniques for the nanosciences andor using nanomaterials in their

work


29

We will continue to develop this work discussed herein and to present this work to a broader audience

These efforts will include the submission of this work for publication in a peer reviewed journal with

the permission of our primary funding sources WorkSafeBC and the Workersrsquo Compensation Board of

Nova Scotia We will also continue to present this work at national and international conferences Our

goals include educating others on the methods available to detect nanoparticle based contamination in

the workplace and to continue the discussion and development of knowledge around the implications of

nanoparticle contamination to workers A key aspect of these on-going discussions is to inspire a larger

discussion and further work on determining the acceptable concentrations of nanoparticle contamination

in the workplace Further efforts are necessary to assess nanoparticle contamination and to correlate it

to the diverse range of nanomaterials being generated world-wide A significant effort has been put into

the generation of nanoscale materials their applications and their potential biological impacts but little

work to date has been put into the detection and remediation of spills containing nanoparticles Our

work highlights this important area and we hope will usher in a new period of discussing this important

consideration for those making handling and otherwise using nanoparticles On-going work in our

group is focused on assisting to establish simple protocols to safely handle nanoparticles other methods

to detect spills of these materials and to communicate the hazards associated with these materials


30

REFERENCES

1 Davis M E Chen Z Shin D M Nat Rev Drug Discov 2008 7 771ndash782

2 Love S A Maurer-Jones M A Thompson J W Lin Y-S Haynes C L Annu Rev Anal

Chem July 2012 5 181ndash205

3 Barth S Hernandez-Ramirez F Holmes J D Romano-Rodriguez A Progress in Materials

Science 2010 55 (6) 563ndash627

4 Hoet P H Bruumlske-Hohlfeld I Salata O J Nanobiotechnology 2004 2 (12) 1ndash15

5 Ji J H Jung J H Kim S S Yoon J U Park J D Choi B S Chung Y H Kwon I H

Jeong J Han B S Shin J H Sung J H Song K S Yu I J Inhalation Toxicology 2007

19 (10) 857ndash871

6 Thomas T Bahadori T Savage N Thomas K Wiley Interdiscip Rev Nanomed

Nanobiotechnol 2009 1 (4) 426ndash433

7 Nel A Xia T Madler L Li N Science 2006 311 (5761) 622ndash627

8 Xia T Li N Nel A E Annu Rev Public Health 2009 30 137ndash150

9 Ostiguy C Soucy B Lapointe G Woods C Meacutenard L Trottier M Health Effects of

Nanoparticles Second Edition No 589 IRSST 2008

10 Thomas K Aguar P Kawasaki H Morris J Nakanishi J Savage N Toxicological

Sciences 2006 92 (1) 23ndash32

11 Lee J H Kuk W K Kwon M Lee J H Lee K Su Yu I J Nanotoxicology May 2013 7

(3) 338ndash345

12 Hamburg M A Science 2012 336 299ndash300

13 ASTM E2535 - 07 Standard Guide for Handling Unbound Engineered Nanoscale Particles in

Occupational Settings 2007

14 Myung C L Park S International Journal of Automotive Technology January 2012 13 (1)

9ndash22


31

15 Buseck PR Posfai M Proc Nat Acad Sci 1999 96 3372ndash3379

16 Calzolaia L Gillilanda D Rossia F Food Additives amp Contaminants Part A 2012 29 (8)

1183ndash1193

17 Giljohann D A Seferos D S Daniel W L Massich M D Patel P C Mirkin C A

Angew Chem Int Ed 2010 49 3280ndash3294

18 Kessler E Environ Health Perspect 2011 119 (3) A120ndashA125

19 Meyer D E Curran M A Gonzalez M A J Nanopart Res 2011 13 (1) 147ndash156

20 Cleveland D Long S E Pennington P L Cooper E Fulton M H Scott G I Brewer T

Davis J Petersen E J Wood L Sci Total Environ April 2012 421ndash422 267ndash272

21 Adamson A W Gast A P Physical Chemistry of Surfaces 6 ed John Wiley amp Sons Inc

New York 1997 293ndash319

22 Becker J S Inorganic Mass Spectrometry - Principles and Applications 1 ed John Wiley amp

Sons Ltd England 2007 255ndash293

23 Evans Analytical (wwwceacom)

24 Shoursheini S Z Sajad B Parvin P Opt Laser Eng 2010 48 (1) 89ndash95

25 Carr R Zhang C S Moles N Harder M Environ Geochem Health 2008 30 (1) 45ndash52

26 Peeters K De Wael K Adriaens A Falkenberg G Vincze L J Anal At Spectrom 2007

22 (5) 493ndash501

27 Laohaudomchok W Cavallari J M Fang S C Lin X H Herrick R F Christiani D C

Weisskopf M G J Occup Environ Hyg 2010 7 (8) 456ndash465

28 Bosco G L Trends Anal Chem 2013 45 121ndash134

29 Estevam M Appoloni C R Health Physics February 2013 104 (2) 132ndash138

30 Jans H Huo Q Chem Soc Rev 2012 41 2849ndash2866

31 Alkilany A M Thompson L B Boulos S P Sisco P N Murphy C J Adv Drug Delivery

Rev 2012 64 190ndash199


32

32 Ye X C Jin L H Caglayan H Chen J Xing G Z Zheng C Vicky D N Kang Y J

Engheta N Kagan C R Murray C B ACS Nano 2012 6 2804ndash2817

33 Choi W I Sahu A Kim Y H Tae G Ann of Biomed Eng 2012 40 534ndash546

34 Nikoobakht B El-Sayed M A Chem Mater 2003 15 1957ndash1962

35 Poon L Zandberg W Hsiao D Erno Z Sen D Gates B D Branda N R ACS Nano

2010 4 6395ndash6403

36 Bakhtiari A B S Hsiao D Jin G X Gates B D Branda N R Angew Chem Int Ed

2009 48 (23) 4166ndash4169

37 Sieb N R Wu N C Majidi E Kukreja R Branda N R Gates B D ACS Nano 2009 3

(6) 1365ndash1372

38 Bogliotti N Oberleitner B Di-Cicco A Schmidt F Florent J-C Semetey V J Colloid

Interf Sci 2011 357 75ndash81

39 Sendroiu I E Warner M E Corn R M Langmuir 2009 25 11282ndash11284

40 Hiramatsu H Osterloh F E Chem Mater 2004 16 2509ndash2511

41 Chassaing E Grand P P Ramdani O Vigneron J Etcheberry A Lincot D J

Electrochem Soc 2010 157 (7) D387ndashD395

42 Gou X L Cheng F Y Shi Y H Zhang L Peng S J Chen J Shen P W J Am Chem

Soc 2006 128 (22) 7222ndash7229

43 Evans C M Cass L C Knowles K E Tice D B Chang R P H Weiss E A J Coord

Chem 2012 65 (13) 2391ndash2414

44 Zhang J Taylor E W Wan X Peng D Int J Nanomedicine 2012 7 815ndash825

45 Wang MCP Gates BD Chem Comm 2012 48 (68) 8589ndash8591

46 Wang MCP Zhang X Majidi E Nedelec K Gates B D ACS Nano 2010 4 2607ndash2614

47 Gates B Mayers B Grossman A Xia Y Adv Mater 2002 14 1749ndash1752


33

48 Lienemann P Bleiner D Proc SPIE 8678 Short-Wavelength Imaging and Spectroscopy

Sources December 2012 86780D

49 Choi S Stassi S Pisano A P Zohdi T I Langmuir 2010 26 (14) 11690ndash11698

50 Kaegi R Voegelin A Sinnet B Zuleeg S Hagendorfer H Burkhardt M Siegrist H

Environmental Science amp Technology 2011 45 (9) 3902ndash3908

51 Nowack B Science 2010 330 1054ndash1055


34

FIGURES AND DATA TABLES

Figure 1 (a) Simulated spill of a 2 L solution containing gold nanoparticles on a section of countertop

as observed by fluorescence microscopy The gold nanoparticles are decorated with a coating of

poly(ethylene glycol) or PEG terminated with a Rhodamine dye (GNR-S-PEG5000-NH-Rhodamine B)

The process of remediating this spill of gold nanoparticles is tracked using (b-d) fluorescence images

and (e) fluorescence spectra (ex = 546 nm) The spill was remediating by wiping the countertop with a

paper towel soaked in water using either (bc) a linear motion or (d) circular motion in a direction

indicated by the yellow arrows relative to the spill (outlined with the yellow dotted line) (e)

Fluorescence spectra obtained by optical microscopy from the original contaminated surfaces and those

surfaces remediated by wiping the spill with a paper towel The background spectrum (eg detector

white noise) is depicted in the purple trace (bottom trace)


35

Figure 2 Remediation of nanoparticle contaminated countertops through the use of casting a polymer

solution onto the surfaces evaporating the solvent and peeling the polymer away from the surfaces

Fluorescence microscopy (ex = 546 nm) of the (a) countertop and (b) polymer film after separating the

polymer from the countertop depict the transfer of the contaminant GNR-S-PEG5000-NH-Rhodamine B

to the cast polymer The remediation process can be monitored by fluorescence spectroscopy where (c)

the fluorescence intensity from the substrate returns to baseline values (equivalent value to that of the

countertop surfaces before contamination) after casting and peeling the fourth polymer film


36

Figure 3 Schematic depiction of the process to use adhesive tape to remediate surfaces contaminated

with nanoparticles The adhesive tape is cast against the contaminated surfaces and subsequently peeled

to remove the nanoparticles that adhere to the tape


37

Figure 4 Data obtained and analyzed by inductively coupled plasma optical emission spectroscopy

(ICP-OES) for silver nanoparticle contamination simulated on a polished silicon wafer The pristine

surface (referred to as clean) establishes the limits of detection for this process The silver nanoparticle

contamination is remediating through a series of up to 15 steps of applying an adhesive tape to the

surfaces removing the tape and repeating this process


38

Figure 5 Peak intensities detected by portable x-ray fluorescence (XRF) spectroscopy for the

remediation of silver nanoparticle contamination as simulated on an isolated section of countertop The

initial countertop (referred to as clean) demonstrates the limit of detection for silver by XRF on the

countertop The other samples depict the detected levels of silver nanoparticles in the simulated

contamination and the associated analysis after each step of the remediation process using an adhesive

tape Error bars on these plots were calculated from multiple measurements on the same substrate to

depict one standard deviation of these measurements


39

Figure 6 Measured peak XRF signals from the analysis of a countertop before (grey bars) and after (red

bars) contamination with silver nanoparticles Each of these two samples was analyzed by rotating the

sample and the portable XRF analyzer relative one another while maintaining the same location of

analysis The peak XRF signal for silver is reported at the initial location (0 degrees) and 90 180 and

270 degrees of rotation


40

Figure 7 Five scans depicting the representative roughness of the countertops used to prepare simulated

contamination by nanoparticles These scans show the profile of the surface roughness by cross-section

Each sample is composed of multiple peaks and recesses of variable height and width


41

Figure 8 Simulated remediation of surfaces contaminated with selenium nanowires (a) A bright

orange colored synthetic rubber is coated onto the contaminated surfaces (in this case the surfaces of a

Canadian 1cent coin) placed on a black countertop (b) The rubber coating is cured and peeled away from

the coin using hand-held tweezers (c) The initial selenium nanowire contamination can be observed by

scanning electron microscopy (SEM) as depicted by the white arrow on the rough surfaces of the coin

(d) Imaging the same region in (c) by SEM analysis following one process of coating and peeling away

the synthetic rubber indicates removal of the selenium nanowires


42

Figure 9 Spectroscopic analysis following the remediation of a simulated spill containing selenium

nanowires on the surfaces of a Canadian 1cent coin Contaminated surfaces were monitored by x-ray

energy dispersion spectroscopy (EDS) The surfaces remediated by casting adhesive tape (red top trace)

contain residual selenium whereas those surfaces remediated by coating with the synthetic rubber

(black bottom trace) show no signs of residual selenium


43

Table 1 Comparison of Selected Methods for the Analysis of Nanoscale Materials dagger

dagger Adapted from Evans Analytical (wwwceacom) and JS Becker Inorganic Mass Spectrometry Principles and Applications John Wiley amp Sons Ltd 2007

Interpretation of abbreviations AES ndash Auger electron spectroscopy EDX ndash energy dispersion X-ray spectroscopy FAAS ndash flame atomic absorption spectroscopy LA-ICP-MS ndash laser ablation inductively coupled plasma mass spectrometry LIBS ndash laser induced breakdown spectroscopy SIMS ndash secondary mass spectroscopy XPS ndash X-ray photoelectron spectroscopy and XRF ndash X-ray fluorescence spectroscopy

method information

provided elements detected

detection limits

analysis time

portable relative

cost

AES chemical

and elemental

Li ndash U 02 gt 1 h no $$$$

EDX elemental Na ndash U 01 gt 1 h no $$$

FAAS elemental Na ndash Bi gt g g-1 gt 1 h no $

LA-ICP-MS

elemental Na ndash U gt ng g-1 minutes no $$$$

LIBS elemental Li ndash U gt g g-1 minutes yes $$

SIMS elemental H ndash U gt ng g-1 gt 1 h no $$$

XPS chemical

and elemental

Li ndash U lt 01 gt 1 h no $$$$

XRF elemental Al ndash U gt g g-1 minutes yes $


44

Table 2 Comparison of Methods for Removing Polymer Films from Countertops

film

support apply heat

peel direction

peel speed

comments

1 no no top-to-bottom

evenly all films came off from the countertop

2 no no corner -to

corner evenly

about 13 of blank sample and most of dye

sample were left on countertop


fast most of NR-PEG-Dye sample and ~15-20

of other 2 samples were left on countertop

4 no no corner -to

corner fast

most of dye sample about 12 of blank

sample and a small corner of NR-PEG-Dye

sample were left on the countertop

5 no yes top-to-bottom


6 no yes corner -to

corner evenly

~15 of blank area of NR-PEG-Dye sample

left on the countertop others came off


fast all films came off from the countertop

8 no yes corner -to

corner fast

most came off from the countertop ~15-20

of blank areas from the NR-PEG-Dye

sample amp dye sample were left on counter

9 yes no top-to-bottom


10 yes no corner -to

corner evenly

most of NR-PEG-Dye sample did not come

off from the countertop other 2 did


fast dye film did not come off from the

countertop other 2 did


corner fast all films came off from the countertop

13 yes yes top-to-bottom


14 yes yes corner -to

corner evenly all films came off from the countertop





This analysis compares samples that included a blank or pristine countertop a countertop coated with the Rhodamine B dye (dye) and countertops coated with GNR-S-PEG5000-NH-Rhodamine B


2

TABLE OF CONTENTS

POINT FORM SUMMARY 3

EXECUTIVE SUMMARY 4-5

MAIN REPORT 6-29

i METHODOLOGY 10-15

ii PROJECT FINDINGSOUTCOMES 15-23

iii IMPLICATIONS FOR FUTURE OCCUPATIONAL HEALTH RESEARCH 23-24

iv APPLICATIONS FOR POLICY AND PREVENTION 24-28

v KNOWLEDGE TRANSLATION AND EXCHANGE 28-29

REFERENCES 30-33

FIGURES AND TABLES 34-44


3

POINT FORM SUMMARY














































exposures)


4

EXECUTIVE SUMMARY
















































5


from the workplace














































6

MAIN REPORT
















The biotoxicity and


the world[8-13]




workplace







7



























nanoparticles




8
























workplace[25-27]







9



























10




















i METHODOLOGY







11










we first



















12
















A typical


gold nanorodsL












13











from pulling apart

















14





























15



























16




























17




nanoparticles























18



























19



























20



















There is also a










21




nanoparticle spills






















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















3

POINT FORM SUMMARY














































exposures)


4

EXECUTIVE SUMMARY
















































5


from the workplace














































6

MAIN REPORT
















The biotoxicity and


the world[8-13]




workplace







7



























nanoparticles




8
























workplace[25-27]







9



























10




















i METHODOLOGY







11










we first



















12
















A typical


gold nanorodsL












13











from pulling apart

















14





























15



























16




























17




nanoparticles























18



























19



























20



















There is also a










21




nanoparticle spills






















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















4

EXECUTIVE SUMMARY
















































5


from the workplace














































6

MAIN REPORT
















The biotoxicity and


the world[8-13]




workplace







7



























nanoparticles




8
























workplace[25-27]







9



























10




















i METHODOLOGY







11










we first



















12
















A typical


gold nanorodsL












13











from pulling apart

















14





























15



























16




























17




nanoparticles























18



























19



























20



















There is also a










21




nanoparticle spills






















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















5


from the workplace














































6

MAIN REPORT
















The biotoxicity and


the world[8-13]




workplace







7



























nanoparticles




8
























workplace[25-27]







9



























10




















i METHODOLOGY







11










we first



















12
















A typical


gold nanorodsL












13











from pulling apart

















14





























15



























16




























17




nanoparticles























18



























19



























20



















There is also a










21




nanoparticle spills






















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















6

MAIN REPORT
















The biotoxicity and


the world[8-13]




workplace







7



























nanoparticles




8
























workplace[25-27]







9



























10




















i METHODOLOGY







11










we first



















12
















A typical


gold nanorodsL












13











from pulling apart

















14





























15



























16




























17




nanoparticles























18



























19



























20



















There is also a










21




nanoparticle spills






















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















7



























nanoparticles




8
























workplace[25-27]







9



























10




















i METHODOLOGY







11










we first



















12
















A typical


gold nanorodsL












13











from pulling apart

















14





























15



























16




























17




nanoparticles























18



























19



























20



















There is also a










21




nanoparticle spills






















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















8
























workplace[25-27]







9



























10




















i METHODOLOGY







11










we first



















12
















A typical


gold nanorodsL












13











from pulling apart

















14





























15



























16




























17




nanoparticles























18



























19



























20



















There is also a










21




nanoparticle spills






















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















9



























10




















i METHODOLOGY







11










we first



















12
















A typical


gold nanorodsL












13











from pulling apart

















14





























15



























16




























17




nanoparticles























18



























19



























20



















There is also a










21




nanoparticle spills






















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















10




















i METHODOLOGY







11










we first



















12
















A typical


gold nanorodsL












13











from pulling apart

















14





























15



























16




























17




nanoparticles























18



























19



























20



















There is also a










21




nanoparticle spills






















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















11










we first



















12
















A typical


gold nanorodsL












13











from pulling apart

















14





























15



























16




























17




nanoparticles























18



























19



























20



















There is also a










21




nanoparticle spills






















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















12
















A typical


gold nanorodsL












13











from pulling apart

















14





























15



























16




























17




nanoparticles























18



























19



























20



















There is also a










21




nanoparticle spills






















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















13











from pulling apart

















14





























15



























16




























17




nanoparticles























18



























19



























20



















There is also a










21




nanoparticle spills






















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















14





























15



























16




























17




nanoparticles























18



























19



























20



















There is also a










21




nanoparticle spills






















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















15



























16




























17




nanoparticles























18



























19



























20



















There is also a










21




nanoparticle spills






















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















16




























17




nanoparticles























18



























19



























20



















There is also a










21




nanoparticle spills






















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















17




nanoparticles























18



























19



























20



















There is also a










21




nanoparticle spills






















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















18



























19



























20



















There is also a










21




nanoparticle spills






















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















19



























20



















There is also a










21




nanoparticle spills






















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















20



















There is also a










21




nanoparticle spills






















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















21




nanoparticle spills






















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















22






















surfaces






23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















23



























24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















24












conditions














25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















25



























26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















26




workplace[1-3]
























27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















27


























28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















28























work


29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















29


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















30

REFERENCES





Science 2010 55 (6) 563ndash627




19 (10) 857ndash871










(3) 338ndash345





9ndash22


31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















31



1183ndash1193















22 (5) 493ndash501







Rev 2012 64 190ndash199


32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















32






2010 4 6395ndash6403


2009 48 (23) 4166ndash4169


(6) 1365ndash1372








Soc 2006 128 (22) 7222ndash7229


Chem 2012 65 (13) 2391ndash2414






33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















33








34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















34













35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















35









36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















36





37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















37







38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















38









39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















39







40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















40





41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















41









42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















42







43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















43




method information


detection limits

analysis time

portable relative

cost

AES chemical

and elemental




LA-ICP-MS




XPS chemical

and elemental




44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly


















44


film

support apply heat

peel direction

peel speed

comments



2 no no corner -to

corner evenly






4 no no corner -to

corner fast






6 no yes corner -to

corner evenly





8 no yes corner -to

corner fast







corner evenly

















detecting, handling and controlling nanoparticle ......detecting, handling and controlling...

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