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Standardization Cosmetics
Why developing standards in cosmetics ?
Why developing ISO standards for analytical methods in cosmetics ?
- To facilitate international trade
- To get the best and safest cosmetic products
- To have common methods between all stakeholders
- To have strong bases for discussion between stakeholders
- To eradicate falsification and bad quality products
For the benefit of all: consumers, producers, traders, regulators
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Standardization Cosmetics
The main criteria for the development of methods is:
QUALITY for safe and pleasant use
Development of methods to insure the quality of
- the cosmetic products
- the ingredients of the cosmetic products
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Standardization Cosmetics
Quality of the ingredients and cosmetic products:
Development of analytical methods to:
- confirm the quality
by the assay of impurities, traces
- avoid the occurrence of analytes of concern
Examples of issues: Nitrosamines, Heavy Metals, Phthalates….
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Standardization Cosmetics
Recurrent international issue: Nitrosamines
ISO standards to avoid
artifacts, false positive results
x
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Standardization Cosmetics
International: ISO (ISO) Technical Committee TC 217
Europe: CEN (EN) Technical Committee TC 392
France: AFNOR (NF) Commission S91K
Edition of: Standards
Technical Specifications (TS)
Technical Reports (TR)
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Standardization Cosmetics
Different and complementary
Working Groups: WG
WG1 Microbiology
WG3 Analytical Methods
WG4 Terminology
WG6 Good Manufacturing Practices
WG7 Sun Products
WG8 Nanomaterials
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Standardization Cosmetics: Analytical Methods
Analytical Methods
Published Standards:
NF ISO 15819:2008: Cosmetics – Analytical methods –
Nitrosamines: Detection and determination of N-
nitrosodiethanolamine (NDELA) in cosmetics by HPLC-MS
NF ISO 10130:2010: Cosmetics – Analytical methods –
Nitrosamines: Detection and determination of N-
nitrosodiethanolamine (NDELA) in cosmetics by post-column
photolysis and derivatization
NF ISO 12787:2011: Cosmetics – Analytical methods –
Validation criteria for analytical results using chromatographic
techniques
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Standardization Cosmetics: Analytical Methods
Standards in progress (ISO):
TR 14000: Cosmetics – Analytical Methods – Nitrosamines:
Technical guidance document on minimising and determining
N-nitrosamines in cosmetics
TR17276: Cosmetics – Analytical approach for screening and
quantification methods for heavy metals in cosmetics
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Standardization Cosmetics: Analytical Methods
New Work in Progress NWIP (ISO):
NWIP: Cosmetics – Analytical methods – Validation criteria for
analytical results using non chromatographic techniques
At the TC level, for repartition of WG workload:
NWIP: Cosmetics – Analytical method – Detection and
quantitative determination of Diethanolamine (DEA) by GC/MS
NWIP: Cosmetics – Guideline on the stability testing of
cosmetics products
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Standardization Cosmetics
How WG3 works for performance verification of the
Analytical methods proposed for Standardization ?
Main approach is by “peer reviews” in experts labs
If problems occur, improvements and performance
verification might lead to interlaboratory tests
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Standardization Cosmetics
Standard ISO 15819:2008
Proposition of revision in 2012
Positive vote for revision on July 2012
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Standardization Cosmetics
ISO10130 further to a collaborative study from CTPA in
Int. J. Cosmetic Sci. 2006
c
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Standardization Cosmetics
Besides the development of analytical methods for standardization, WG3 develops Technical Reports
TR14000 on minimising Nitrosamines in cosmetics
Report on
- analytical methods (screening to quantitative)
- formulation guidances
for avoidance of the formation of Nitrosamines
Publication awaited in the forthcoming weeks……
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Standardization Cosmetics
TR17276 on Heavy Metals
Report on available analytical methods
for testing, screening, quantitate
heavy metals in cosmetics and ingredients
first step for the future development of standards
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Standardization Cosmetics
ISO 12787:2011
Validation criteria for analytical results in cosmetics
Confidence in performance, reliability and quality
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Standardization Cosmetics
Background and Rationale for ISO12787 standard
Cosmetics are very diverse with an extensive area of various products
perfumes, creams, shampoos, lipsticks, mascara, powders, soaps, toothpastes….
How far can we obtain validation data for a single method to be considered as pertinent and suitable for use for cosmetics, including finished products and ingredients ?
ISO12787 gives a procedure for validation criteria
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Standardization Cosmetics
ISO12787 gives a procedure for validation criteria
for analytical results using chromatographic methods
ISO12787 allows to extend the use of an analytical method known as suitable for a cosmetic matrix to another cosmetic matrix
The ISO12787 standard describes 3 steps
- 1st step: Study on standard solutions
- 2nd step: Screening sample
- 3rd step: Assay
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Standardization Cosmetics
Aim of ISO12787:
to ensure the sample assay results
ISO12787 is particularly beneficial
- for the determination of analytes in various and complex matrices
(i.e. cosmetics)
- when a full method validation is not appropriate or cannot be achieved (too many different matrix samples to analyze)
- when it is not possible to make reconstituted sample matrices
v
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Standardization Cosmetics
1st Step: Suitability study using standard solutions
- Determine the quantification limit in solvent
- Check the calibration range linearity
- Check the system conformity
All necessary specificity parameters such as resolution, asymmetry, selectivity..
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Standardization Cosmetics
2nd Step: Screening
Evaluation of the analyte content (estimated value)
Two cases:
- samples detected without analyte or with analyte content such as the s/n ratio is low
- samples detected with analyte content such as the s/n ratio is > 10
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Standardization Cosmetics
3rd Step: Assay
Depending the results of the former screening step:
- If no detection: ensure the absence of detection of the analyte depending following cases:
- assays are performed with a target value
- assays are performed without any target value
- If the analyte has been detected - obtain an assay result with different suitable and sufficient validation parameters to ensure its validity
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Standardization Cosmetics
Example of tests to be performed for results validation
using the 3 steps procedure:
standard solutions, sample screening, assay
Validation criteria
using Standard
solution
Sample
screening
Assays
1st step 2nd step 3rd step Analyte not detected
or with a s/n < LoQ
Analyte detected
with s/n > LoQ Assays with spike
recovery
Assays using a
target value
Solvent standard
calibration levels
5 (LoQ)
+
15 (53) Linearity
5 5
Unspiked samples 1 1 1 1 (3) a Spiked samples
(before treatment)
i.e. PrEMS
3 1 1 (2) a
Spiked sample
(after treatment)
i.e. PoEMS
1
Check standard 1 1 a If a RSD or a confidence interval is to be determined on the final assay result
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Standardization Cosmetics: Analytical Methods
CEN Standards:
EN 16217: Methods for analysis of allergens – Quantification
of suspected fragrance allergens in consumer products. Step
1 – GC analysis of ready to inject samples
Standardization Cosmetics: Analytical Methods Determination of allergens
24 allergens detected and quantified by GC/MS Allergens regulated in the EU
Standardization Cosmetics: Analytical Methods Determination of allergens
•Coeluted compound
•(Non common ions)
•Rs>1.5
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Standardization Cosmetics: Analytical Methods
Standards in final phase (CEN):
prEN 16342: Cosmetics — Analysis of cosmetic products —
Quantitative determination of zinc pyrithione, piroctone olamine and
climbazole in surfactant containing cosmetic anti-dandruff products
prEN 16343: Cosmetics — Analysis of cosmetic products —
Determination of 3-iodo-2-propynyl butylcarbamate (IPBC) in
cosmetic preparations, LC-MS methods
prEN 16344: Cosmetics — Analysis of cosmetic products —
Screening for UV-filters in cosmetic products and quantitative
determination of 10 UV-filters by HPLC
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Standardization Cosmetics: Analytical Methods
New Work in Progress (CEN):
NWI: Cosmetics – Analysis of cosmetic products - GC/MS method for
the identification and assay of 12 phthalates in ready to inject
cosmetic samples
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Cosmetics EU Regulation
In Europe
Annexes to Directive 76/768/CEE and Regulation 1223/2009
lists of ingredients/impurities that are
- forbidden (ex: CMR compounds…)
- or regulated (ex: UV filters, conservatives…)
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European Commission
Seven Directives on Analytical Methods
First Commission Directive 80/1335/EEC of 22 December 1980 on the
approximation of the laws of the Member States relating to methods of
analysis necessary for checking the composition of cosmetic products
[Amended by Directive 87/143/EEC, Official Journal L 383 of 31.12.1980]
Second Commission Directive 82/434/EEC of 14 May 1982
[Amended by Directive 90/207/EEC, Official Journal L 185 of 30.06.1982]
Third Commission Directive 83/514/EEC of 27 September 1983
Fourth Commission Directive 85/490/EEC of 11 October 1985
Fifth Commission Directive 93/73/EEC of 9 September 1993
Sixth Commission Directive 95/32/EC of 7 July 1995
Seventh Commission Directive 96/45/EC of 2 July 1996
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Standardization Cosmetics
Discussion at the European level
to actualize the Methods “Directives”
to replace them by Standards
in line with the new Regulation 1223/2009 to
be implemented on July 11, 2013
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Standardization Cosmetics
Some other good reasons
to develop standardized methods….
Identification of …….
…..”False Medicines”,
presented as cosmetics
…..Cosmetic Falsifications
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Skin whitening products / « false medicines »
Methods for Hydroquinone & corticosteroïdes survey
Hydroquinone Arbutine Acide kojique Acide azélaïque
Clobetasol propionate Fluocinonide Betamethasone dipropionate
Hydroquinone and Corticosteroïdes
are banned in cosmetics in the EU
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Skin whitening products / « false medicines »
Methods for Hydroquinone & corticosteroïdes survey
Corticosteroides Retention time
(min) Unadjusted relative retention
Triamcinolone 3,86 0,42
Prednisolone 4,49 0,49
Cortisone 4,58 0,50
Hydrocortisone 4,65 0,51
Bétaméthasone base
Triamcinolone acetonide
5,52 coeluted
0,60
Dexamethasone
Desonide
5,68 coeluted
0,62
Desoximetasone
Fluocinolone acetonide
6,29 coeluted
0,68
Prednisolone acétate
Flurandrenolide
6,92 coeluted
0,75
Hydrocortisone acétate 7,32 0,80
Hydrocortisone butyrate
Budesonide1
Methylprednisolone acétate
7,98 coeluted
0,87
Betaméthasone acétate 8,33 0,91
Budesonide2
Dexamethasone acétate
9,13 Coeluted with ISTD
1,00
Hydrocortisone valérate
Hydrocortisone aceponate
9,85 coeluted
1,07
Fluocinonide 10,83 1,18
Diflorasone diacétate 11,52 1,26
Betamethasone valerate 11,89 1,30
Amcinonide 12,50 1,36
Difluprednate 13,04 1,42
Prednicarbate 13,74 1,50
Alclometasone dipropionate 14,08 1,54
Halcinonide 14,92 1,63
Mometasone furoate
Betamethasone dipropionate
15,40 coeluted
1,68
Clobetasol propionate 16,30 1,78
Beclomethasone dipropionate 18,93 2,07
Prednisolone hexanoate 20,96 2,29
Flumethasone pivalate 25,10 2,74
Fluocortolone pivalate 27,55 3,01
Difluocortolone valérate 28,56 3,12
Clocortolone pivalate 31,05 3,43
Fluocortolone -hexanoate 37,04 4,05
Butylparaben (ISTD) 9,13 1,00
Development of methods for Hydroquinone,
Hydroquinone esters and corticosteroïdes survey
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Standardization Cosmetics
ISO WG3 experts
65 experts registered
expertise diversity: industry, regulation, standardization, academy
20 member states: Brazil, Spain, France, USA, India, UK, Germany, Columbia, Japan, Jordan, Korea, Poland, Australia, South Africa, China, Sweden, Sri Lanka, New Zealand, Nigeria, Czech Republik
Regular meetings (2 / year) since 2000 (creation of ISO/TC217)
WG3 meeting in Jeju Fall 2008