Determination of Lead Content in Clinique, Covergirl, and LA Expression Brand Lipsticks using Inductively
Coupled Plasma-Optical Emission Spectroscopy, Inductively Coupled Plasma-Mass Spectrometry, and
Atomic Absorption Spectroscopy
Farrah Y. Qureshi, University of Colorado at Boulder Department of Chemistry
Spring 2011
A crash-course in cosmetics: lipstick
According to a 2004 study
(14), 81% of American
women use lipstick
What is lipstick?
•
•
•
A viscoplastic material
used to enhance shape,
sheen, and color of the
lips.
Composed of Lamellar
structures
Different “finishes” have
different compositions of
waxes, oils, emollients,
colors, and
minerals/shimmer
Lead: a heavy metal
HEALTH EFFECTS
•
•
•
•
•
•
Reproductive disorders
High Blood Pressure
Hypertension
Nerve disorders
Memory problems
pain
FDA LIMITS IN CANDY
0.1 ppmm
no upper limits in cosmetics
What did the FDA find?
•The
FDA study found that 60%
of lipsticks contained some lead
(1, 4).
• Studies in Saudi Arabia found
up to 4000 ppmm lead in lipstick
(2,3).
Procedure published in J. Cosmet.
Sci.
Performed using HF/Boric Acid
Microwave Assisted Digestion and
analyzed in ICP-MS
Brand name
Cover Girl
Revlon
Parent
company
Lipstick
Line
and Shadea
Procter &
Gamble
Incrediful
Lipcolor
964
Maximum
Red
Revlon, Inc.
ColorStay
Lipcolor
345 Red
Velvet
Lot
numbersb
Lead (Pb)c
(ppm)d
7241S1
3.06
5188S1
3.05
Composite
e
2.91f
07298
2.38
Cover Girl
Procter &
Gamble
Queen
Collection
Q580 Ruby
Remix
7136
2.24
Body Shop
L'Oreal
Lip Colour
22 Garnet
C274EA
1.79
Cover Girl
Procter &
Gamble
Continuous
Color
435 Cherry
Brandy
7228
1.76
L'Oreal
L'Oreal
Colour
Riche
315 True
Red
FD261
1.47
Revlon
Revlon, Inc.
Super
Lustrous
660 Bed of
Roses
07208 150
8 53
1.37
Maybelline
L'Oreal
Moisture
Extreme
F315 Cocoa
Plum
WD2891
1.21
How does lead get into cosmetics?
Maybe it’s born with it, maybe it’s manufacturing
Color additives and shimmer
Each color additive can have 20 ug/g of lead
• Galena can be added to shimmer or affixed to
mica in lipstick
•
Manufacturing and production
Solder
• Leaded paints on manufacturing equipment
• Lead-contaminated dust
•
The Samples
•Covergirl
Lip Perfection
•Smitten
•Soulmate
•Clinique’s
A Different Lipstick
•Rasberry
Glace
•Spiced Apple
•LA
Color Expression
•Cocoa
•Coral
•Burt’s
Bees
Shimmer
Experimental Procedure
The digestion
Samples between 0.30.5 g of lipstick were
added to a sample
vial; blanks were
prepared using Burt’s
Bees
Samples were
dissolved in
concentrated trace
metal grade nitric acid
and heated overnight.
Concentrated
hydrogen peroxide
(30%) was added to
the samples and the
samples were heated.
The samples were
diluted to 10 mL and
filtered for glitter and
wax
Instrumental Method 1: Atomic
absorbance
0.6
Conditions:
10% Nitric Acid, Lead Nitrate,
217.0 nm
0.5
Absorbance (AU)
Initially, no results
All values read below zero or at
zero, including instrument
spikes.
y = 0.0334(+/-0.003)x - 0.03(+/-0.02)
R² = 0.971
0.4
0.3
0.2
0.1
0
-0.1
0
5
10
Concentration (ppm)
15
20
Atomic Absorbance: Part 2
The Chelation Conundrum
0.45
0.4
0.35
absorbance (AU)
Adding disodium EDTA
improves the signal
dramatically; however, all values
are under the LOD and LOQ—
difficult to determine if noise or
lead atoms.
The linearity of the calibration
curve also increased.
y = 0.0146(+/-0.0005)x + 0.0078(+/-0.005)
R² = 0.9948
0.3
0.25
0.2
0.15
0.1
0.05
0
0
5
10
15
Concentration (ppm)
20
25
Method 2: ICP-OES
Inductively Coupled Plasma-Optical Emission Spectrometry
All values found were below
detection limit of instrument,
including instrument spike of
~30 ppm.
Speculations as to what’s going
on:
•Matrix effects
•Formation of lead oxides,
sulfides, or binding to
hydrocarbons present in
solution
Why do the mechanisms of AAS and
OES not work on this matrix?
•http://web.uvic.ca/ail/techniques/Jablonski.jpg
ICP-MS Data
Inductively Coupled-Mass Spectrometry
Concentration of Lead (ppmm)
Concentration of Arsenic (ppmm)
LA Expressions: Cocoa Shimmer, Trial 1
55.8413+/‐0.0003
11.00+/‐0.01
Clinique's A Different Lipstick: Raspberry Glace, T1
0.2480+/‐0.0003
Covergirl Lip Perfection: Smitten, Trial 1
0.0165+/‐0.0002
0.06+/‐0.01
Blank‐Burt's Bees
0
‐‐
Covergirl Lip Perfection: Soulmate, Trial 2
1.036+/‐0.0003
‐‐
Discussion of Results
Sources of error: 411 on the 404
•Different
energies to overcome
in samples
•Uneven
dissolution and heating
•Different compositions lead to
deviations in volume
•Hydrogen
peroxide addition step
caused some samples to “erupt”
•Product
loss
•Product
loss in filtration of
glitters and waxes
•Metals could still be bound to
waxes
•Uneven dilution factors
•Contaminants from lab
•Dust,
pipettes, etc.
Discussion of Results
Experimental Revisions
•Addition
of disodium EDTA
dihydrate to beginning of
digestion
•Facilitation
of chelation
•Larger
beakers to prevent
eruptions of hydrogen peroxide
and nitric acid
•Larger initial lipstick samples to
increase detection limits
•Lower temperature of heating of
peroxide/acid mixture
•Longer
heating
•Less chance of eruption
Future Works
•Analysis
lipsticks
of other heavy metals in
•Cadmium,
arsenic, mercury
•Analysis
of heavy metals in other
cosmetics
•Eye shadow, eyeliner/kohl/kajal,
, mascara, lip gloss, foundations,
blush, etc.
•A
study to see how intense
matrix effects affect heavy metal
penetration of the dermis
•If
matrix effects are so large, will
metals be released under normal
conditions
•Amalayze,
HCl exposure
References
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Questions?