TITLE
DETERMINATION OF PHTHALATES
GLOBAL LABORATORY NUMBER
0006-7420
REVISION
B
DATE
2/2/2009
OPERATING PROCEDURE AUTHOR
Ying Gao REVISED BY
Ying Gao
1 SCOPE
1.1 Products and Components Covered（产品和包含组分）
1.1.1 1.1.2 1.1.3 1.1.4 1.1.5 1.1.6 1.1.7 1.1.8 1.1.9 1.1.10 1.1.11 1.1.12 1.1.13 plastic parts（塑胶部件）
glues/adhesives（胶水和胶黏剂）
cosmetics（化妆品）
synthetic rubber（合成橡胶）
sealants（密封剂）
lubricants（润滑剂）
solids in aerosols（固体气溶胶）
foamed plastics（泡沫塑胶）
modeling clay（粘土模型）
fragranced/scented items（芳香和香水类）
surface coatings（表面涂层）
off set printing inks（印刷油墨）
raw materials falling under the scope of GQMP 2116, PHTHALATES CONTROL FOR
MATTEL OWNED OPERATED PLANTS.  This requirement applies to Mattel Owned
Operated Plants Only.
1.2 Exemptions（豁免）
1.2.1 1.2.2 1.2.3 Packaging materials intended to be discarded（废弃包装材料）.
Batteries included for try-me purposes(电池类)
Inaccessible materials in products intended for the adult collector (does not include fashion dolls)（成人收藏品）
1.3 Definitions (Words that are defined are italicized and bolded once per section)
buchiSurface coating:  All layers of materials such as paint or similar, that dries to a solid film when it is applied to a surface and that can be scraped off with a sharp blade or washed off with a
solvent such as acetone or ethanol, without removing substrate (base) material
Composite Sample:  A sample made from combining more than one material or color, e.g.,
paint (red, yellow, and blue); vacuum metalized coating (silver and gold).  It is not considered compositing when colors or materials can not be separated (e.g., thin stripes, doll eyes).
1.4 Purpose
This procedure describes the general process for soxhlet extraction and analysis of di-n-butyl phthalate (DBP), butyl benzyl phthalate (BBP), di (2-ethylhexyl) phthalate (DEHP), di-n-octyl
phthalate (DNOP), di-isononyl phthalate (DINP), di-isodecyl phthalate (DIDP), and di-n-Hexyl phthalate( DnHP) in various samples.
2 TEST METHODS
2.1 Test
Environment
(not applicable)
2.2 Safety Information
2.2.1 2.2.2
2.2.3 2.2.4 2.2.5
2.2.6 2.2.7
2.2.8
2.2.9 2.2.10
2.2.11 Splash goggles should be worn when using solvents.
Phthalate are suspected cancer agents, possible teratogens and reproductive hazard. Adequate precautions must be taken to avoid undue exposure. Wherever possible, all steps of the analytical process must be conducted in a well ventilates fume hood. The analyst is also directed to were protecti
ve gloves, and use mechanical pipetting devices while handling all working solutions or concentrates.
Vapor inhalation of solvents can irritate the respiratory tract and may cause dizziness, coughing, and headaches.  Use these solvents in a well ventilated area.
Skin contact of solvents can cause irritation, redness, and drying.  Only handle these solvents with chemical resistant gloves.
Solvent vapors can irritate the eyes and splashing can sting and cause pain and redness.  It is required to wear splash goggles when using the solvents.
If solvent contacts the skin or eyes, flush immediately with large quantities of water.
The acids and solvents should be stored in separate cabinets.  Keep the solvents in a flammable cabinet and the acid in an acid resistant cabinet.  Storing the acids and solvents together is hazardous.
The waste generated should be handled as hazardous waste and should be disposed of in accordance with local hazardous waste regulations.
Ensure that the laboratory is equipped with an emergency eyewash station and a spill kit.  Additional q
uestions regarding workplace safety can be referenced in Part 8 (Workplace Safety) of the Mattel Global Manufacturing Principle Standards.
Any Environmental, Health and Safety concerns can be directed to Rodney Davis at rodney.davis@mattel or at 310-252-4894.
Safety glasses should be worn when scraping.
2.2.12
2.2.13 2.2.14
2.2.15 Cut resistant gloves are required when using the blades for scraping.
Blades should be disposed of in a separate designated container and not in the general trash.
When using knifes or blades, follow the practices listed below to prevent injuries: •Never cut toward any part of your body.
•Always cover or store away the blade when the knife is not in use.
•Keep your blade sharp. A dull blade must be forced to do its work and makes the tool hard to control.
•Always use the right knife for the job. If you are cutting heavy material, use a larger blade. Trying to cut heavier material with a smaller blade can cause you to lose
control of the knife.
•Always try to use the knife on a flat surface.
• Always keep your attention focused on what you are cutting. Even a slight distraction
can cause a serious injury.
2.3 Apparatus and Equipment
• Gas Chromatography with Mass Spectrometer (GC-MS), or equivalent
• DB5-MS, 30m x 0.25mm ID, 0.25 μm, J&W or equivalent
• Electronic analytical balance capable of weighing to 0.0001g
• 150ml stoppered flat-bottomed flask
• Soxhlet extractor with siphon cup
• Soxhlet cellulose thimble
• Fast extraction system, Foss Soxtec 2055 Fat extraction system, Buchi B-811or equivalent • Rotary evaporator, Buchi R215, Brinkman, or equivalent
• Glass syringe, Hamilton or equivalent. (10µl, 50µl, 250µl, 500µl and 1000µl)
• Less than 0.5 μm membrane filter ( Whatman, Millipore or equivalent)
• 25ml volumetric flask
• Surgical scalpels, stainless steel
• Scissors, stainless steel
• Forceps
• Other labware
2.4 Chemicals and Reagent
• Dichloromethane(CH 2Cl 2, DCM), GC analysis grade
• Acetone(C 3H 6O) ultra resi-analysed grade
• Phthalate Standards, ChemService or equivalent
2. butyl benzyl phthalate (BBP)
4. di-n-octyl phthalate (DNOP)
5. di-isononyl phthalate (DINP)
6. di-iso-decyl phthalate (DIDP) Substances CAS No.
1. di-n-butyl phthalate (DBP) 84-74-2
85-68-7 3. di(ethylhexyl) phthalate (DEHP) 117-81-7
117-84-0 28553-12-0
26761-40-0 7. di-n-Hexyl phthalate( DnHP) 84-75-3
2.5
General Test Requirements
• Avoid the use of any type of plastic labware (e.g. wash bottle) to prevent contamination. • Before each analysis, the glassware must be rinsed with acetone free of phthalates.
• All of solvent must be analysed that they are free of any phthalates.
• Raw GCMS data from all blank, samples and spikes must be evaluated for interference.
Determine if the source of interference is in the preparation and /or cleanup of the samples and take corrective action to eliminate the problem.
• To reduce carryover, the sample syringe must be rinsed with solvent between sample
injections. Whenever an unusually concentrated sample is encountered, it should be followed by the analysis of solvent to check for cross-contamination.
• Analyze materials separately whenever possible.
• A composite sample (of no more than 3 materials) is allowed when sufficient sample to
conduct the testing cannot be collected from 12 samples.
• Samples are to be tested in the same form they appear on the finished product, e.g. paint is
tested in its dry state.
• Test frequency is per the following:
• GQMP 0006-2116, Phthalates Control for Mattel Owned Operated Plants
• GQMP 0006-2117, Phthalates Control for Mattel OEM and Specialty Vendors
2.6 Procedure
2.6.1    2.6.1.1.1 2.6.1.1.2 2.6.1.1.3 2.6.1.2.1 2.6.1.2.2 Standard preparation
Standard solutions can be prepared from pure standard materials or purchased as
certified solutions.
2.6.1.1 1% (10000 mg/L) Individual standard stock solutions
Weigh 0.1g (100mg) of each standard into a 10ml beaker
respectively.
Dissolve with small amount of DCM, ultrasonic if necessary.
Transfer into a 10ml volumetric flask separately and fill up to the
mark with DCM.
2.6.1.2 Calibration standard solutions for GC-MS analysis
According to Table1, prepare calibration solutions of DBP, BBP,
DEHP, DnHP, DINP, DNOP and DIDP mixture
Make up to the 10ml mark with DCM.
Note: The below calibration standard ranges are for reference. The linear
range of phthalates may not be same for each GCMS system.
Set 1 – DBP, BBP, DEHP, DnHP, DNOP, DINP, and DIDP calibration solutions(mg/L)
Analytes Standard 1 Standard 2 Standard 3 Standard 4
DBP 2 5 10 20 BBP 2 5 10 20 DEHP 2 5 10 20 DnHP 2 5 10 20
DNOP 2 5 10 20 DINP 20 50 100 200 DIDP 20 50 100 200
Table1. Preparation of calibration standard solutions
2.6.1.3    Standard spike solutions                                        2.6.1.
3.1    According to Table 2 below, prepare a separate set of
standard spike solutions which are:
1.
DBP, BBP, DEHP, DnHP, DNOP mixture 2.
DIDP 3. DINP
2.6.1.
3.2 Make up to the mark to 10 ml with DCM.
2.Set 3  Phthalates 6.1.
T
Table2. Preparation of each set of standard spike solutions
Vol.  of 1% individual stock solution, ml Final Volume, ml
Concentration, mg/L DBP 0.5
BBP 0.5
DEHP 0.5 DNOP 0.5
1 DnHP 0.5
10 500
2 DIDP 0.5    5 1000
3 DINP 0.5    5 1000  Note:  All pure standards and stock standard solutions are stored at -10 ºC or less or as
recommended by the standard manufacturer. Transfer the stock standard solutions into
bottles with PTFE-lined screw-caps.
All standard solutions must be stored at 4 ºC and replaced after 6 months or sooner if
comparison with quality control check samples indicates a problem.
Calibration verification standard should be prepared weekly and stored at 4 ºC.
2.6.2 Sample Preparation
Homogenous material of a particular color shall be sampled from all available locations
of the sample and mixed to give a sample size of at least 0.5g.  More than one sample
may be sampled to obtain enough weight.  Any contamination would affect the test result.  Proper cleaning technique, before and after each sample, must be used to reduce the
risk of contamination. The spatulas, glass rods, glass plates, surgical scalpels, razor
blades and forceps shall be cleaned with acetone and wiped dried with tissue paper
before use and between each sample.
2.6.2.1 Solid sample
For a solid sample, use a scalpel or other appropriate cutting utensils to cut the
representative portions from the sample into small pieces, approximately 2mm x
2mm, collect it into a clean container and mix well.
2.6.2.2 Liquid sample
For a liquid sample such as paint and ink, Shake the sample well and / or stir thoroughly using a clean spatula or glass rod.
2.6.2.2.1 2.6.2.2.2 2.6.2.
3.1 If the liquid samples are not volatile, spread a thin film of the sample onto the glass plate. Place the glass plate into a drying oven (105 ± 5ºC) until the sample is dried, If the sample is not completely dried after 2 hours, stop the drying process and go to the next step with the semi-dried paint. Scrape the dried or semi-dried sample using a razor blade or a surgical scalpel into a clean container.
For liquid sample which are volatile or semi-volatile, dissolve aliquot sample into DCM and shake well, if necessary, ultrasonic for 5 – 20 minutes. Transfer a portion of solution and filter it through 0.22 μm membrane filter. Transfer a portion to a 1.5ml injection vial ready to be injected into GC-MS.
2.6.2.3 Surface Coating
Coatings on Hard Plastic, Textile or Coated paper
Scrape surface coating gently from the substrate using a surgical
scalpel or a razor blade onto a glass plate.  Care should be taken to
prevent scraping of any base material.
2.6.2.
3.2 Coatings on Soft Plastic or Leather.
Before attempting the solvent washing method, test a non-coated
section of base material by wiping with the selected solvent.  If no
change on the base material is observed, solvent washing method is
applicable.
2.6.2.
3.2.1    Solvent washing by 1:1 Acetone / Ethanol: Place approximately 10 – 15
ml of the selected solvent into a pre-weighed 25 ml beaker. Roll a piece
of cotton into a ball, grasp with forceps, and soak it with the selected
solvent. Swab off the surface coating lightly with the cotton ball. If 1:1
acetone/ethanol washing attacks the substrate, use an ethanol wash
only.  Signs the substrate material is attacked by the solvent include:
•When the substrate color is different from the coating and is visible in the removed surface coating.  For example, yellow paint is applied
to blue plastic.  When removing the coating, if a blue color is visible
in the sample removed, plastic was picked up with the coating.
•If contamination is suspected, then the sample should be prepared again from the beginning.
If the coating does not dissolve in 1:1 acetone/ethanol, use acetone
wash only or undergo solvent loosening by acetone method. Re-
dissolve the paint from the cotton ball with the appropriate solvent into
the beaker.  The paint may be re-dissolved by swishing the cotton ball in
the solvent.  The cotton ball may then be used to remove more coating
from the sample.  When finished removing the coating from the sample,
squirt the cotton ball with the solvent to remove the last of the coating
from the cotton ball. Blow the solution to dryness with a hair dryer or dry
in a drying oven (at 105 ± 5°C). Allow the sample to cool to room
temperature.