Cosmetics of one form or another have been used since the beginning of time. The U.S. FDA has not regulated metals in cosmetics except in the case that zirconium is prohibited in aerosol preparations and mercury can only be used (generally as a preservative) when no other alternative is possible. They do have the authority to protect consumers against contamination deemed to be deleterious to health. Proposition 65 in California requires notice when concentrations in a product may cause exposure to hazardous components exceeding a prudent level. A letter from the Attorney General of the State of California discusses the level of concern and calculates that based on documented lipstick use, a concentration of 5 mg/kg would be the level of concern requiring listing. The regulations in Canada include statements about heavy metals, and although low concentrations may be difficult to avoid, concentrations above the levels listed in Table 1 (page 2 of Application Note) require special scrutiny.

1. A P P L I C AT I O N N O T E
ICP-Mass Spectrometry
Authors
Zoe Grosser, Ph.D.
Lee Davidowski, Ph.D.
Laura Thompson
PerkinElmer, Inc.
Shelton, CT 06484 USA
The Determination of Introduction
Cosmetics of one form or another have
Metals in Cosmetics been used since the beginning of time.
The U.S. Food and Drug Administration
(FDA) defines today’s cosmetics as:
“1. articles intended to be rubbed, poured, sprinkled, or sprayed on, introduced
into, or otherwise applied to the human body or any part thereof for cleansing,
beautifying, promoting attractiveness, or altering the appearance, and 2. articles
intended for use as a component of any such articles; except that such term
shall not include soap.” 1
The U.S. FDA has not regulated metals in cosmetics except in the case that zirconium
is prohibited in aerosol preparations and mercury can only be used (generally as
a preservative) when no other alternative is possible. They do have the authority
to protect consumers against contamination deemed to be deleterious to health.
Proposition 65 in California requires notice when concentrations in a product
may cause exposure to hazardous components exceeding a prudent level. A
letter from the Attorney General of the State of California discusses the level
of concern and calculates that based on documented lipstick use, a concentration
of 5 mg/kg would be the level of concern requiring listing.2 The regulations in
Canada include statements about heavy metals, and although low concentrations
may be difficult to avoid, concentrations above the levels listed in Table 1 (Page 2)
require special scrutiny.

2. Measurements in this work are performed using ICP-MS.
Table 1. Canadian metal concentrations of concern in
Elements chosen for examination are commonly considered
cosmetics.3
to be toxic, although there are others that might be consid-
Metal Concentration (mg/kg) ered hazardous as well, such as antimony, included on the
Lead 10 Canadian list.
Arsenic 3
Cadmium 3 Experimental
Mercury 3 Samples of a variety of commercially available lipsticks
Antimony 5 (Figures 1 and 2), nail polishes, and skin creams (for evening
tone, lightening age spots) were purchased and prepared in
duplicate. Nail polishes were painted onto tared weighing
The European Union (EU) has also developed a list of more
paper and allowed to dry before weighing into the digestion
than 1000 compounds that are banned for use in cosmetic
vessel (Figures 3 and 4). Microwave digestion was used
manufacturing. They further limit the amount of these
(Multiwave™ 3000, PerkinElmer®, Shelton, CT USA) to obtain
compounds that may be found naturally-occurring in the
clear solutions. Six mL of nitric and 0.5 mL of hydrofluoric
product. For example, strontium peroxide may be found in
acid (GFS Chemical™, Columbus, OH USA) were added to
rinse-off hair care preparations, but is limited to containing
Teflon™ vessels with approximately 0.3-0.5 g of sample and
less than 4.5% as strontium in the ready-to-use product.4
the digestion program shown in Table 2 applied. The samples
Examining the notices of recall in the U.S. for products were then transferred and diluted to 50 mL with ASTM®
manufactured in various parts of the world show that a Type I water. The samples were fairly homogeneous and in
number of items which have been recalled are cosmetics. a form that allowed a representative sample to be easily
For example, skin whitening cream from several Caribbean taken. If the samples were solids, grinding, blending or other
countries was put on an import alert because the level of procedures might be necessary to ensure a more homogeneous
mercury measured in the product was 8%.5 Another alert sample to be measured. Preparing replicate samples will allow
was issued for eye colors including Kohl, Kajal, or Surma. us to evaluate if our homogeneity assumption is accurate.
In addition to being an unapproved coloring agent, the
material was found to contain lead (Pb). There has also been Table 2. Microwave digestion program.
recent concern about lead in lipstick, uncovered through Step Power Ramp Hold Fan
testing.6 The U.S. FDA has not recalled lipstick and states 1 750 10:00 10:00 1
they will do further testing.7 The guidance mentioned for
2 1200 10:00 10:00 1
lead relates to the limited guidance available for food,
where a letter stating that 0.1 mg/kg of Pb in candy is the 3 0 15:00 3
maximum tolerable limit for acceptable children’s exposure.
An ELAN® DRC-e ICP-MS (PerkinElmer, Shelton, CT USA)
This application note will evaluate the levels of several was used for measurement of chromium, cadmium, lead,
heavy metals in lipstick, nail polish and skin cream. Based mercury, arsenic, selenium, and antimony. The instrumental
on candy guidance in the U.S. and the limits set in Canada, conditions are shown in Table 3 (Page 3). Mercury was also
either graphite furnace atomic absorption (GFAA), inductively measured using the SMS 100 Mercury Analyzer (PerkinElmer,
coupled plasma optical emission spectroscopy (ICP-OES), Shelton, CT USA) which uses a combustion system, requiring
or inductively coupled plasma mass spectrometry (ICP-MS) no sample preparation and generating no waste. Instrumental
would be appropriate, based on the amount of sample conditions are shown in Table 4 (Page 3).
taken for digestion and the final volume of solution.
Figure 1. A variety of commercially- Figure 2. Lipstick was weighed prior Figure 3. Nail polish was dried on Figure 4. The nail polish and tared
available lipsticks were analyzed. to microwave digestion. tared paper before digestion. paper were weighed into the
digestion vessel.
2

3. Table 3. ICP-MS instrumental conditions. Table 4. Mercury system instrumental conditions.
Nebulizer Quartz Concentric Parameter
Spray Chamber Quartz Cyclonic Dry 400 °C for 200 s
RF Power 1500 W Decomposition 800 °C for 350 s
Integration time 1000 ms (per analyte) Catalyst 600 °C
Replicates 3 Catalyst wait period 60 s
Reaction Gas for arsenic O2 = 0.6 mL/min Gold trap 600 °C for 30 s
RPq for arsenic as 91 AsO 0.5 Measurement 100 s
Oxidant gas flow 350 mL/min
Arsenic analysis employed cell technology to remove the
chloride interference arising from either natural chlorine
Results and Discussion
content, salt added to a supplement material or hydrochloric
acid used in sample preparation, which can degrade the Sample preparation is an important contributor to the
detection limit. This cell allows a gas to react with the results, especially when it influences the consistency and
sample, and under controlled conditions, the interference is information provided by the results. An article by several
chemically separated from the analyte. Figure 5 shows how researchers, including the U.S. FDA, discussed the need
the Dynamic Reaction Cell™ (DRC™) operates. Detection for a small amount of hydrofluoric acid (HF) in the digest
limits are improved compared to other approaches and the to ensure better consistency and recovery of all the metal,
precision in varying matrices is more consistent. An instrument including that which might be protected from other acid
detection limit for arsenic measured in 1000 mg/L NaCl was attack by a silica particle.9 The question always becomes:
shown to be 2.3 ng/L, comparing favorably to detection is it better to report the total metal content or the portion
limits of 0.6-1.8 ng/L, measured in 1% nitric acid solution, that might be bioavailable? Even if lipstick is consumed and
using this technique.8 exposed to hydrochloric acid in the digestion process, lead
enclosed in silica particles will not be released and is there-
fore unable to cause harm. The digestion here used HF and
therefore reports a total metal value with more confidence,
although it may not be all bioavailable.
Several performance criteria were evaluated to ensure the
method was operating as expected and the sample prepara-
tion had been performed correctly. Table 5 (Page 4) shows
the results for NIST® reference material Typical Diet (1548a)
digested at the same time as the cosmetics, using the same
conditions and acids. Although Typical Diet is not a cosmetic
matrix, it has some of the same components. The fat content
may not be comparable to all of the skin cream or lipstick
Figure 5. Dynamic reaction cell (DRC) operates with the PerkinElmer
ELAN® ICP-MS to react and remove interferences without allowing types, depending on their formulation.
competing reactions to add other interferences.
The mass for selenium measurement was chosen to avoid
interference from calcium, which may be present in cosmetics.
Since this work was completed, the NexION® 300 ICP-MS
has been introduced by PerkinElmer, Inc. and performance
is expected to be the same or better than the ELAN DRC-e
ICP-MS.
3

4. Table 5. NIST® 1548a Typical Diet certified reference material.
Element and Mass 1548a – 1 (mg/kg) 1548a – 2 (mg/kg) Average (mg/kg) Certificate Value % Rec
Cr 52 0.135 0.118 0.127 –
Cd 111 0.036 0.038 0.037 0.035 106
Hg 202 < DL < DL 0.005*
Pb 208+207+206 0.045 0.046 0.046 0.044 104
Se 82 0.231 0.251 0.241 0.245 98.4
AsO 91 0.183 0.192 0.188 0.20 93.8
Prepared at the same time as the cosmetics, using the same procedure.
* Informational value, not certified.
Recoveries of the certified values were within ±20%, indicating
acceptable performance. Table 6. Estimated detection limits in the solid cosmetic.
Element and Mass µg/g
Detection limits were estimated from digested blanks run
Cr 52 0.044
during the analysis. The standard deviation was multiplied
by three and adjusted by the dilution of the solid during Cd 111 0.00069
digestion to give an estimate in the original cosmetic material. Hg 202 0.0037
Estimated detection limits calculated for the solid cosmetic Pb 208 0.0096
material are well below the current compliance limits, allowing
Se 82 0.082
confidence when measurements are made near the compliance
AsO 91 0.014
limits.
The duplicate digestions were run and average values
reported in Table 7 for the lipsticks. It is interesting to note
that although several have more than 1 µg/g of lead (which
caused a controversy when results were reported in the
Poison Kiss document10), it is below the regulated limit in
Canada. Other elements that may be of concern are also
seen in some samples, such as Cr and Se.
Table 7. Lipstick results (ug/g).
Element Lip-1 Lip-2 Lip-3 Lip-4 Lip-5 Lip-6 Lip-7 Lip-8 Lip-9 Lip-10 Lip-11 Lip-12
and Mass
Cr 52 7.41 7.05 93.3 0.226 18.7 0.858 7.94 5.27 0.645 0.520 1.46 1.46
Cd 111 0.0293 0.0179 0.139 0.0353 0.0264 0.00860 0.0398 0.144 0.0288 0.00897 0.0159 0.00595
Hg 202 0.00944 0.00794 < DL < DL 0.00977 0.0125 0.0107 < DL 0.00707 0.00422 < DL < DL
Pb 208 1.38 0.545 0.273 0.0407 0.611 1.12 0.591 0.397 0.321 0.943 0.489 0.700
Se 82 0.211 < DL < DL < DL 0.329 0.162 < DL 0.708 1.91 105 0.166 0.108
AsO 91 0.828 0.250 0.411 0.481 0.073 0.123 0.209 0.242 0.0571 0.0586 0.0976 0.0969
Table 8 shows the individual results for two sample
Table 8. Precision and agreement of duplicate samples (µg/g).
digestions for Lipstick 3 and standard deviation
and relative percent difference (RPD) between Element and Mass Lip-3 A Lip-3 B Average SD RPD
the two measured concentrations. The RPD is less Cr 52 94.4 92.2 93.3 01.52 2.30
than 5%, which shows good agreement between Cd 111 0.138 0.140 0.139 0.00129 1.31
the duplicate digestions. Hg 202 < DL < DL < DL –
Pb 208 0.271 0.275 0.273 0.00221 1.15
Se 82 < DL < DL < DL –
AsO 91 0.421 0.401 0.411 0.0142 4.90
4

5. The lipsticks covered a range of colors, from black to pink,
red, purple and brown. The results for the elements measured Table 10. Skin cream results (µg/g) and post-digestion spike
varied quite a bit between the various brands and colors. recovery.
The black lipstick (Lip-4) was made in China and was one of Element Cream-1
the lipsticks lowest in lead and the other metals measured. and Spike
In no case was the Canadian limit or the limit suggested in Mass Cream-1 Cream-2 Cream-3 Recovery (%)
California for Proposition 65 compliance exceeded. Cr 52 0.0318 0.0800 0.00867 109
Cd 111 0.00318 0.00122 0.00194 87.6
Several of the lipsticks measured in the Poison Kiss publication10
Hg 202 < DL < DL < DL 111
were also purchased for this work. The result obtained here
for lead on Lipstick 5 was 0.611 µg/g and in the report on Pb 208 < DL 0.168 0.0180 97.2
two separate tubes of lipsticks they measured 0.65 and Se 82 0.0198 0.168 0.187 –
0.50 µg/g. The measurements in the publication were also AsO 91 < DL 0.0128 < DL 86.4
performed using ICP-MS, but the digestion used contained
Sb 121 0.00187 0.00483 0.0120 92.4
nitric and sulfuric acid and no HF. Therefore, the results may
Spike levels in solution: 4 µg/L, except mercury 0.5 µg/L
be low or may have less precision for duplicate measurements.
Another cosmetic with a different kind of matrix is nail polish Post-digestion spike recoveries show that the matrix is not
and a variety of colored nail polishes of different brands unduly influencing the accuracy of the result.
were measured for the same elements and the results are
shown in Table 9. Colors ranged from blue to pink and Lead was measured on two separate days, at least a week
red. Again, small amounts of metals are present in most of apart, to ensure the results could be replicated (Table 11).
the polishes and may cause exposure if nails are bitten or The lead results were present at several different concentration
chewed and the polish ingested. levels in the skin cream and showed good agreement over
the two days.
Table 9. Nail polish results (µg/g).
Element NP-1 NP-2 NP-3 NP-4 NP-5 NP-6 Table 11. Lead results on separate days (µg/g).
and Mass Cream-1 Cream-2 Cream-3
Cr 52 6.58 0.999 2.95 0.800 10.9 1.96 Day 1 < DL 0.168 0.0180
Cd 111 0.0364 0.0290 0.0193 0.0160 0.0832 0.0110 Day 2 < DL 0.161 0.0214
Hg 202 < DL < DL 0.00965 < DL 0.192 0.00826
Pb 208 0.863 0.947 2.12 0.204 6.03 1.82 Skin cream has been the subject of a U.S. FDA Import Alert
Se 82 62.2 128 161 61.7 0.0477 0.397 because high mercury content was found in potential import
samples. Mercury measurements were confirmed for the
AsO 91 0.147 < DL 0.266 0.0690 1.91 0.510
skin creams measured in this work using a dedicated mercury
system (Table 12). The detection limit is lower than with
The third type of cosmetic examined was skin cream. This digestion because dilution is less and low concentrations of
type of skin cream was intended to lighten the skin to remove mercury were confirmed. Small samples can be used and
age spots or even skin tone. Three types were digested and rapid screening performed because the system requires no
measured for the elements of interest. Antimony was added sample preparation and generates no waste. Figure 5 shows
as an analyte for this determination to show that it can be the autosampler for the mercury system and the sample
incorporated into the multielement run for Canadian compli- measured into small boats.
ance. The results are shown in Table 10.
Table 12. Mercury results using mercury system.
Conc. (µg/g) SD
Cream-1 < DL
Cream-2 0.00240 0.00008
Cream-3 0.00824 0.000044
Three replicate analyses averaged
Detection limit: 0.02 ng/g in the skin cream
Figure 5. Skin cream samples measured into small boats for analysis.
5

6. Conclusions References
Cosmetics contain a variety of components that can be 1. Food, Drug, and Cosmetic Act, as amended through 2004,
challenging to digest, including fats and silica-based compounds. Chapter II, Definitions 21USC 321, http://www.fda.gov/
Digestion using a microwave with the addition of HF to digest opacom/laws/fdcact/fdcact1.htm.
siliceous materials may be necessary. Sensitivity to the resulting
decisions to be made with the information, such as the need 2. Letter from Edmund G. Brown, Attorney General, State of
for bioavailability information, may influence the sample California, to two law groups in reference to Proposition
preparation acids chosen. Microwave digestion also provides 65 Claims Concerning Lead in Lipstick, http://ag.ca.gov/
a clean digestion and retains mercury so that a full suite of prop65/pdfs/Lipstick_Letter-a.pdf (accessed 1-24-2011).
elements may be easily examined.
3. Draft Guidance on Heavy Metals in Cosmetics, Health
ICP-MS is a good choice for determination of low concentrations Canada, http://www.hc-sc.gc.ca/cps-spc/legislation/consul-
of analytes, allowing evaluation of toxic and potentially toxic tation/_cosmet/metal-metaux-consult-eng.php (accessed
components in cosmetics. More sophisticated interference 1-24-2011).
correction, such as DRC, can remove molecular interferences
4. Cosmetic Products Regulation, EU Regulation 1223/2009
at the mass of interest, allowing the lowest detection limit to
(accessed 1-24-2011).
be achieved.
5. Import Alerts, http://www.fda.gov/ForIndustry/Color
This application note has demonstrated the successful analysis of
Additives/ComplianceEnforcement/EnforcementNews/
three types of cosmetics for toxic elements and shown good
ucm123909.htm (accessed 1-24-2011).
results through replicate analyses and spiked samples. Analysis
of a reference material helped to ensure that the digestion 6. Lead in Lipstick http://www.safecosmetics.org/article.
step and instrumental analysis were under control. php?id=223 (accessed 1-24-2011).
Acknowledgement 7. FDA Q&A, http://www.fda.gov/Cosmetics/ResourcesFor
You/Consumers/CosmeticsQA/default.htm (accessed 1-24-
The authors would like to thank Lindsay Drennan for the
2011).
confirmatory data on mercury in skin cream measured with
the SMS 100 Mercury Analyzer. 8. Ruth Wolf and Ken Neubauer, Determination of Arsenic in
Chloride Matrices, PerkinElmer, (2002).
9. N.M. Hepp, W.R. Mindak, and J. Cheng, J. Cosmet. Sci.,
60, 405–414 (July/August 2009).
10. A Poison Kiss: The Problem of Lead in Lipstick, The
Campaign for Safe Cosmetics, October 2007 http://www.
safecosmetics.org/downloads/A%20Poison%20Kiss_report.
pdf (accessed 1-24-2011).
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