chemistry & cosmetics - spex certiprep...© spex certiprep, inc. 2011 elements measured element...
TRANSCRIPT
© SPEX CertiPrep, Inc. 2011
Patricia Atkins
Product Applications Specialist
Chemistry & Cosmetics Analysis of Lipstick for Toxic Elements using ICP-MS
© SPEX CertiPrep, Inc. 2011
Housekeeping
Everyone in attendance today will receive a copy of the
presentation slides
The webinar is being recorded and will be posted to our
YouTube account about one week after the event
Questions will be answered at the end of the presentation
– Type any questions you may have into the question box
and we will answer them during the Q & A portion
© SPEX CertiPrep, Inc. 2011
History
Cosmetics have historically contained
toxic compounds
Egyptian cosmetics: Pb & Hg
– Kohl: burnt almonds, oxidized
copper, different-colored copper ores, lead, ash, arsenic
compounds & ochre
– Mesdemet: copper and lead ore
Greek & Romans
– White complexion = Pb
– Red colors = Cinnabar = Hg
– Brows = Stibium = Sb
© SPEX CertiPrep, Inc. 2011
History
Medieval & Renaissance
– White Pale Complexion
= Mask of Youth
• Used by men &
women
• Hydroxide, carbonate
& Pb oxide
– Elizabeth I
• Covered acne and pox
scars with heavy white
makeup
© SPEX CertiPrep, Inc. 2011
History
20th century
– Radium cosmetics & personal
products = ‘healthy glow’
• 1918
– Avg Salary = $1500
– Hourly wage= $0.30-$0.70
– Year rent $178
– $2 Compact = >$50 today
• 1930’s
– Radioactive materials
• 1950’s to today
– Spas with Radon
http://www.cosmeticsandskin.com
© SPEX CertiPrep, Inc. 2011
History
Modern products perception-
no toxic compounds
– Recalls on FDA
– Various problems from
physical to bacterial
contamination
Cosmetics used around the
globe
Generates hundreds of
billions of dollars of revenue
© SPEX CertiPrep, Inc. 2011
FDA regulates cosmetic industry
– No premarket approval for
finished cosmetics
– Regulates limits on additives &
colorants
Hepp et. Al = up to 3 ppm Pb
This study examines the lipstick
for a wide range of compounds
and re-examines the Pb level
Correlations examined between
colors, finish type and elemental
levels
Studies & Regulations
© SPEX CertiPrep, Inc. 2011
Chemistry of Lipstick
Base
– Waxes
– Oils
• Castor Oil
Preservatives
– Vitamins
– Antioxidants
Flavors
Finish components
– Esters – shine
– Micas - shine
Pigments & Colorants
© SPEX CertiPrep, Inc. 2011
Chemistry of Lipstick
Pigments & Colorants
– Organic Colorants
• Coal Tar colorants
– must undergo safety
testing
– only ingredients required
by FDA
• FD&C colors – safe for
internal & external use
• External D&C – external use
– Inorganic Colorants in Lipstick
• Iron Oxide Black
• Iron Oxide Red
• Iron Oxide Orange
• Iron Oxide Yellow
• Iron Oxide Brown
• Manganese Violet
© SPEX CertiPrep, Inc. 2011
Samples
48 Products from SPEX
CertiPrep Employees
Age: new to several years old
Price Range: $5 to $35 per
container
14 Brands
Products:
• Lip stains
• Lip gloss
• Lip balm
• Lipstick
© SPEX CertiPrep, Inc. 2011
Samples (cont.)
Beige/Tan (3)
Brown (7)
Light Pink (3)
Dark Pink (7)
Corals/Peaches (11) Berry/Wine (11)
White/Colorless (6)
48 Samples
© SPEX CertiPrep, Inc. 2011
Samples (cont.)
Metallic
Four types of finishes
Pearlescent Pearlescent
Matte Metallic Clear
Three physical state types
–Solid
–Semi-solid
–Liquid
© SPEX CertiPrep, Inc. 2011
Materials
SPEX CertiPrep Standards:
• CLMS-1: Multi Element Solution Standard 1
• CLMS-2: Multi Element Solution Standard 2
• CLMS-3: Multi Element Solution Standard 3
• CLMS-4: Multi Element Solution Standard 4
• Base Oil 20 Standard
Reagents:
• High Purity Nitric Acid
• High Purity Hydrofluoric Acid
• 4% Boric Acid Solution
© SPEX CertiPrep, Inc. 2011
Sample Preparation
Hepp, N. M., Mindak, W. R., and Cheng,
J., Journal of Cosmetic Science, Vol. 60,
No. 4, July/August, 2009.
Samples digested in CEM Mars 5
Microwave Unit
– XP-1500 Vessels
– two-step microwave digestion
procedure
© SPEX CertiPrep, Inc. 2011
Sample Preparation (cont.)
Step 1:
– 0.3 g of sample
– 7 mL high purity Nitric Acid
– 2 mL high purity HF
– Microwave Program:
• Ramp to 130°C over 15
minutes; hold 3 minutes
• Ramp to 200°C over 15
minutes; hold 30 minutes
• Allow to cool
© SPEX CertiPrep, Inc. 2011
Sample Preparation (cont.)
Step 2:
– 30 mL of 4% high purity
Boric Acid solution
– Microwave Program:
• Ramp to 170°C over
15 minutes; hold 10
minutes
Diluted to 50 mL DI H2O
Digestion blanks run prior
to sample digestion
Diluted 1000x prior to ICP-
MS analysis
© SPEX CertiPrep, Inc. 2011
Instrument Conditions
Instrumentation
– Macroelement analysis:
• PerkinElmer ICP-OES
Optima 7300
– Trace element analysis
• Agilent ICP-MS 7700
– Meinhard nebulizer
– Cyclonic spray chamber
– Analysis performed
• normal mode: air
• collision mode: Helium
Condition Setting
Power 1550 W
Plasma Gas 15 L/min
Aux Gas 0.3 L/min
Nebulizer 0.80 L/min
Sampling Rate 0.3 mL/min
© SPEX CertiPrep, Inc. 2011
Elements Measured
Element Gas Mode Line Element Gas Mode Line
Ag Air 107, 109 Ni He & Air 60
Al Air & He 27 Os Air 189
As Air & He 75 P Air 31
Au Air 197 Pb Air 206-208
Ba Air 135-137-138 Pd Air 105
Be Air 9 Pr Air 141
Ca He 44 Pt Air 195
Cd He 111-113 Rb Air 85
Ce Air 140 Re Air 187
Co Air & He 59 Rh Air 103
Cr Air & He 52&53 Ru Air 101
Cs Air 133 Sb Air 121, 123
Cu He 63 Sc He 45
Cu He 63 Se He 77
Fe He 56 Si He 30
Ga Air 71 Sm Air 147
Gd Air 156 Sn He & Air 117-120
Ge He 74 Sr He & Air 86 & 88
Hf Air 178-180 Ta Air 181
Hg Air 201 Tb Air 159
Ho Air 165 Te Air 125
In Air 115 Th Air 232
Ir Air 193 Ti Air 47
K He 39 Tl He 203, 205
La Air 139 Tm Air 169
Li Air 7 U Air 238
Lu Air 175 V He 51
Mg Air 24 W Air 182
Mn He 55 Y Air 89
Mo Air 95,97,98 Yb Air 172
Na Air 23 Zn He 66
Nd Air 146 Zr Air 90
© SPEX CertiPrep, Inc. 2011
Results: Trace Elements
Precious metals and rare elements found in small
amounts
– Ag = 0.21 ppm
– Au = 0.22 ppm
– Pt = 0.74 ppm
Correlations between colors
– Ag = Peach color; exclusively one brand
– Au = Browns and Berries; multiple brands, one
predominant
– Pt = Whites and Browns but not in Berries;
predominate in one brand
– Pd = Berries & Dark Pinks
Correlation between finishes
– Au = Metallic not Pearls
– Ag = Pearls not Metallic
– Ir = Pearls not Metallic
Element Avg (ppm) Max (ppm)
Ag 0.04 0.21
Au 0.02 0.22
Cu 1.47 7.20
Ga 2.01 4.28
Gd 0.03 0.15
Ge 0.25 1.37
Hf 0.15 1.13
In 0.07 0.95
Ir 0.47 3.62
La 0.40 1.29
Nd 0.07 0.68
Pd 0.02 0.10
Pr 0.01 0.10
Pt 0.03 0.74
Re 0.00 0.04
Rh 0.03 0.21
Se 0.13 0.52
Sm 0.03 0.13
Ta 0.86 1.90
Th 0.06 0.27
W 3.04 8.63
Y 0.07 0.26
Yb 0.01 0.04
© SPEX CertiPrep, Inc. 2011
Results: Macroelements
Very high Al, Ca, K levels
– Concern over Al?
Expect large amounts of Fe, K,
Mg, Si, Ti
Element Avg (ppm) Max (ppm)
Al 38283.69 360,790.97
Ba 2734.56 26,494.60
Ca 28248.93 345,753.07
Fe 8262.90 63,177.23
K 11917.92 128,129.69
Li 19.51 144.52
Lu 107.65 335.41
Mg 610.38 5,566.33
Mn 20.52 90.38
Na 380.01 2,962.92
P 13.36 97.81
Rb 22.94 82.00
Sc 3.90 101.37
Si 13387.93 47,661.39
Sn 21.77 359.28
Sr 30.28 255.13
Ti 14664.03 38,477.15
Zn 40.13 1,084.94
Zr 8.10 39.37
© SPEX CertiPrep, Inc. 2011
Results: Macroelements (cont.)
0
20,000
40,000
60,000
80,000
100,000
120,000
140,000
160,000
Al Ca Fe K Si Ti
Co
nce
ntr
ati
on
(p
pm
)
Macroelement
White
Lt Pink
Dk Pink
Coral
Berry
Tan
Brown
© SPEX CertiPrep, Inc. 2011
Results: Macroelements (cont.)
0
200
400
600
800
1,000
1,200
1,400
1,600
1,800
Mg Mn Zn Zr
Co
nce
ntr
ati
on
(p
pm
)
Macroelement
White
Lt Pink
Dk Pink
Coral
Berry
Tan
Brown
© SPEX CertiPrep, Inc. 2011
Results: Macroelements (cont.)
Correlation with Color
– Darker colors, higher concentrations
• Cu
• K
• Mn
• Se
• Low Zr
• Low Si
• Al
• Ca
• Si
• Zn
• Cu • K
• Mn
• Se
• Al
• Ca
• Si
• Zn
• P
• Zr • W
• Low Ca
© SPEX CertiPrep, Inc. 2011
Results: Macroelements (cont.)
Matte
Metallic
Pearlescent
Correlation with Finish Type
© SPEX CertiPrep, Inc. 2011
Results: Toxic Elements
Pb cited up to 3 ppm (Hepp et al)
– Our max = 2.4 ppm
– Avg = 1 ppm
Highest potentially toxic or
hazardous elements
– Cr = 31 ppm
– Ni = 23 ppm
– V = 51 ppm
– Sb = 10 ppm
Low ppb levels found of Cd, Hg &
U
Element Avg Min Max
As 0.30 0 0.69
Be 0.49 ND 1.23
Ce 0.24 ND 3.37
Co 0.44 ND 4.30
Cr 2.44 0 31.45
Cs 1.68 ND 4.76
Mo 0.27 0 4.12
Ni 2.88 0 23.36
Pb 0.96 ND 2.39
Sb 0.33 ND 9.58
Tl 0.08 ND 0.23
V 4.68 ND 50.72
© SPEX CertiPrep, Inc. 2011
Results: Toxic Elements (< 1ppm)
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
As Be Ce Mo Tl
Co
nce
ntr
ati
on
(p
pm
)
Trace Element
White
Lt Pink
Dk Pink
Coral
Berry
Tan
Brown
© SPEX CertiPrep, Inc. 2011
Results: Toxic Elements (<10 ppm)
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
Co Cr Cs Ni Pb Sb W
Co
nce
ntr
ati
on
(p
pm
)
Trace Element
White
Lt Pink
Dk Pink
Coral
Berry
Tan
Brown
© SPEX CertiPrep, Inc. 2011
Results: Toxic Elements (<100 ppm)
0.00
10.00
20.00
30.00
40.00
50.00
60.00
70.00
80.00
90.00
100.00
Sn Sr V
Co
nce
ntr
atio
n (
pp
m)
Trace Element
White
Lt Pink
Dk Pink
Coral
Berry
Tan
Brown
© SPEX CertiPrep, Inc. 2011
Results: Toxic Elements (cont.)
• V
• As • V
• Sr
• As
• Pb
• Tl
• Pb
• Sr
• Pb
• Sr
Correlations with Color Higher concentration = Darker colors
© SPEX CertiPrep, Inc. 2011
Results: Toxic Elements (cont.)
Pearlescent
Matte
Metallic
Correlation with Finish Type
© SPEX CertiPrep, Inc. 2011
What does this mean?
Exposure & Human Limits
The EPA RfD – is the oral reference dosage
defined as: ‘…an estimate … of a daily exposure
to the human population (including sensitive
subgroups) that is likely to be without an
appreciable risk of deleterious effects during a
lifetime…expressed in units of milligrams per
kilogram of bodyweight per day (mg/kg/day).’
WHO - The TDI is an estimate of
the amount of a substance in food
or drinking-water, expressed on a
body weight basis (mg/kg or μg/kg
of body weight), that can be
ingested daily over a lifetime
without appreciable health risk.
© SPEX CertiPrep, Inc. 2011
Exposure
Element
Max
Concentration in
Lipstick (ug/g)
ug in 0.10 g
lipstick
EPA or WHO RfD
(ug/kg/day)
Calculated Rfd for
163-lb (74 kg)
Adult Female
(ug/kg)
Amount of lipstick
needed to exceed
RfD (g)
As 0.88 0.0088 4 296 334.54
Ba 26494.60 264.9460 200 14800 0.56
Be 1.17 0.0117 2 148 126.28
Cd 0.04 0.0004 1 74 1684.66
Cr 31.45 0.3145 3 222 7.06
Hg 0.08 0.0008 0.1 7.4 87.49
Ni 23.36 0.2336 20 1480 63.35
Pb 2.39 0.0239 3.6 266.4 111.39
Sb 9.58 0.0958 0.4 29.6 3.09
Sr 109.24 1.0924 600 44400 406.43
Tl 0.21 0.0021 0.1 7.4 34.66
U 0.05 0.0005 3 222 4639.80
V 36.43 0.3643 9 666 18.28
© SPEX CertiPrep, Inc. 2011
Exposure
Element
Amount of tubes of
lipstick consumed in
one day to exceed RfD
Ba 0.25
Sb 1
Tl 11
Hg 30
Pb 37
As 111
Cd 560
© SPEX CertiPrep, Inc. 2011
Conclusions
Many elements found
present in lipstick
Toxic elements
–Pb found up to 2 ppm
–Very Low Hg, Cd
found
Very High amount of Al
© SPEX CertiPrep, Inc. 2011
Conclusions
The highest concentrations of
elements in darker colors
Light colors, glosses or balms
have lowest concentrations
The exposure rate to the toxic
elements is very small
Large amounts of lipstick would
have to be consumed to reach
RfD levels
© SPEX CertiPrep, Inc. 2011
Acknowledgements
Thanks to all the employees of SPEX CertiPrep &
SamplePrep
Huifang Lang, Chemist, SPEX CertiPrep
Lazlo Ernyei, ICP Chemist, SPEX CertiPrep
Bill Driscoll, ICP-MS Chemist, SPEX CertiPrep
Vanaja Sivakumar, VP Inorganics, SPEX CertiPrep
Method by Hepp, N. M., Mindak, W. R., and Cheng, J., Journal of
Cosmetic Science, Vol. 60, No. 4, July/August, 2009.
© SPEX CertiPrep, Inc. 2011
Questions?
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New in 2011
Visit www.spexcertiprep.com for more information!
2011-2012 Catalog – Now
available on CD!
New Consumer Safety
standards kit for USP 232 (Part# USP-TXM1)
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