Part 1: The Sample Preparation of Imported Plastic Toys for the Analysis of BPA & Phthalates - Patricia Atkins SPEX CertiPrep
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Part 1: The Sample Preparation
of Imported Plastic Toys for the
Analysis of BPA & Phthalates
Patricia Atkins
SPEX CertiPrep
1
© SPEX CertiPrep, Inc. 2012
Housekeeping
Everyone will receive a copy of the presentation slides
The webinar is being recorded and will be posted to our
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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 session
Stick around after the Q & A session for details on your
chance to win a Keurig Coffee Maker!
© SPEX CertiPrep, Inc. 2012
Part 1: Sample Preparation
Introduction & Background on Plastics
Plastic Identification
Sample Preparation Techniques and
Methods
Overview of the CPSC PVC method
Snapshot of findings
© SPEX CertiPrep, Inc. 2012
Part 2: Sample Extraction & Analysis
Offered June 7th at 10AM and 2PM
– Email with registration next week
Details about CPSC method
Extraction methods development
Microwave methods optimization
Comparison to CPSC PVC method
GCMS Analysis
Detailed Findings
© SPEX CertiPrep, Inc. 2012
In the News
© SPEX CertiPrep, Inc. 2012
The Best Reason to Study
Phthalates
© SPEX CertiPrep, Inc. 2012
Phthalates
Background Uses
• Produced since late 1800’s • Plastic compounds
• Commercial use in 1920’s (10-60% by wt)
• Binders
• Coatings
• Fragrances and pigments
Health Effects Response
• US ban children’s toys
• Residue is widespread
2009
• Variety of disorders:
• Mexico, the EU, and Japan
asthma, reproductive
restricted or banned the
• Endocrine disruptor use of phthalates in
children’s toys
© SPEX CertiPrep, Inc. 2012
Common Phthalates
Name Acronym Structural formula CAS No.
Dimethyl phthalate DMP C6H4(COOCH3)2 131-11-3
Diethyl phthalate DEP C6H4(COOC2H5)2 84-66-2
Diallyl phthalate DAP C6H4(COOCH2CH=CH2)2 131-17-9
Di-n-propyl phthalate DPP C6H4[COO(CH2)2CH3]2 131-16-8
Di-n-butyl phthalate DBP C6H4[COO(CH2)3CH3]2 84-74-2
Diisobutyl phthalate DIBP C6H4[COOCH2CH(CH3)2]2 84-69-5
Butyl cyclohexyl phthalate BCP CH3(CH2)3OOCC6H4COOC6H11 84-64-0
Di-n-pentyl phthalate DNPP C6H4[COO(CH2)4CH3]2 131-18-0
Dicyclohexyl phthalate DCP C6H4[COOC6H11]2 84-61-7
Butyl benzyl phthalate BBP CH3(CH2)3OOCC6H4COOCH2C6H5 85-68-7
Di-n-hexyl phthalate DNHP C6H4[COO(CH2)5CH3]2 84-75-3
Butyl decyl phthalate BDP CH3(CH2)3OOCC6H4COO(CH2)9CH3 89-19-0
Di(2-ethylhexyl) phthalate DEHP C6H4[COOCH2CH(C2H5)(CH2)3CH3]2 117-81-7
Di(n-octyl) phthalate DNOP C6H4[COO(CH2)7CH3]2 117-84-0
Diisodecyl phthalate DIDP C6H4[COO(CH2)7CH(CH3)2]2 26761-40-0
n-Octyl n-decyl phthalate ODP CH3(CH2)7OOCC6H4COO(CH2)9CH3 119-07-3
Diisononyl phthalate DINP C6H4[COO(CH2)6CH(CH3)2]2 28553-12-0
© SPEX CertiPrep, Inc. 2012
6 Restricted Phthalates
Name Acronym Structural formula CAS No.
Di-n-butyl phthalate DBP C6H4[COO(CH2)3CH3]2 84-74-2
Butyl benzyl phthalate BBP CH3(CH2)3OOCC6H4COOCH2C6H5 85-68-7
Di(2-ethylhexyl) phthalate DEHP C6H4[COOCH2CH(C2H5)(CH2)3CH3]2 117-81-7
Di(n-octyl) phthalate DNOP C6H4[COO(CH2)7CH3]2 117-84-0
Diisodecyl phthalate DIDP C6H4[COO(CH2)7CH(CH3)2]2 26761-40-0
Diisononyl phthalate DINP C6H4[COO(CH2)6CH(CH3)2]2 28553-12-0
© SPEX CertiPrep, Inc. 2012
Regulations & Banned Phthalates
DEHP DBP BBP DINP DIDP DNOP
0.1% 0.1% 0.1%
individual individual individual 0.1% 0.1% 0.1%
CPSIA
US CPSC-CH-C1001-09.03
(All toys & (All toys & (All toys & individual individual individual
Childcare) Childcare) Childcare) (Oral Contact) (Oral Contact) (Oral Contact)
0.1% combined 0.1% combined
EU EC Directive 2005/84/EC
(All toys) (Toys with Oral Contact)
ST Standard Part 3 / 0.1% combined 0.1% combined
Japan Food Sanitation Law (All toys) (Toys with Oral Contact)
© SPEX CertiPrep, Inc. 2012Bisphenol A
Background Uses
• 3.7 million metric • Polymers
tons/yr • Coatings and epoxy
• Reported in 1891 resins
Health Effects Regulations
• Suggested estrogenic • The EPA guideline - 50
effects in the 1930’s µg/kg/day
• Endocrine disruptor • As low as 0.025
µg/kg/day can have
adverse effects
© SPEX CertiPrep, Inc. 2012Regulations
Area Scope of BPA Ban Requirement
No National Ban;
US Various childcare products
State by State
EU PC baby bottles Banned
PC baby bottles Banned
Canada
BPA deemed toxic Action
© SPEX CertiPrep, Inc. 2012Testing Method for Phthalates
CPSC-CH-C1001-09.03
Standard Operating Procedure for
Determination of Phthalates
(Children’s Toys & Childcare Articles)
Measurement of 6 Restricted
Phthalates
Outlines:
• Sample Preparation
• Extraction
• Analysis
© SPEX CertiPrep, Inc. 2012Toy Samples
26 Toys
‘Dollar’ stores
Items with Oral Contact:
• Whistles
• Snorkels
• Baby cup
• Funny teeth
Items with possible oral
contact:
• Army men
• Rubber duck
• Doll head
© SPEX CertiPrep, Inc. 2012Sample Preparation: Separation
26 Toys
>65 samples
Stickers were removed
Paint was not removed
• Metals testing =
remove paint when
possible
© SPEX CertiPrep, Inc. 2012Sample Preparation: Grinding
CPSC Method < 2 mm or grind
using cryogenic methods to
powder
SPEX SamplePrep 6970 Freezer
Mill
• Multi-Vial Adaptor
• 6751 Vials
Polycarbonate vials used,
stainless steel vials also available
© SPEX CertiPrep, Inc. 2012Grinding Tips General Program Program 2.5 grams of plastic Precool = 20 minutes Pieces cut to
Sample Preparation: Grinding
Cryogenic grinding allows for a fine analytical powder not possible with
room temperature grinding.
© SPEX CertiPrep, Inc. 2012Particle size & Extraction
Decreased particle size > surface
area
CPSC = 5mm
5 mm
Random 2-5 mm
2 mm
Ground Samples
Samples extracted using
microwave extraction
Samples extracted by wet method
© SPEX CertiPrep, Inc. 2012Grinding and Extraction Efficiency
Microwave Extraction
5 mm 2 mm Powder
© SPEX CertiPrep, Inc. 2012Grinding and Extraction Efficiency
CPSC Wet Method
2 mm Powder
© SPEX CertiPrep, Inc. 2012Sample Preparation: Grinding Tips
Factors to consider when grinding
Polycarbonate Vials
• Possible polymer carryover
• Blank QC sample eliminates
contamination concerns
Stainless Steel Vials
• Metal contamination possible if
following up with metals analysis
• Blank QC sample eliminates
contamination concerns
© SPEX CertiPrep, Inc. 2012Sample Preparation: Grinding Tips
Factors which affect grinding:
Size
• Too Large – inhibits
movement
• Too Small – limits impact
Shape
• Fibrous material – need
smaller vessels and more
cooling
• Round, spherical beads –
bounce, need additional
cooling
© SPEX CertiPrep, Inc. 2012Sample Preparation: Grinding Tips
Factors which affect grinding:
Type of Polymer
• Melting Point of polymers effect grinding times
• Low melt polymers can create sticky residue
which inhibit even grinding unless extra cooling is
used
Melting Point (oC)
PP 130-171
PE 105-130
LDPE 105-115
HDPE 120-130
ABS >80
PC Glass state: 150 Melt state: 267
PVC 100-260* additives used
© SPEX CertiPrep, Inc. 2012Sample Preparation: Grinding Tips
© SPEX CertiPrep, Inc. 2012Methods for Plastic Identification
FT-IR: ASTM E1252:
– Standard Practice for General Techniques for Obtaining Infrared
Spectra for Qualitative Analysis
Thermogravimetric Analysis (TGA): ASTM E1131
– Standard Test Method for Compositional Analysis by
Thermogravimetry
Differential Scanning Calorimetry (DSC): ASTM D3418
– Standard Test Method for Transition Temperatures and Enthalpies
of Fusion and Crystallization of Polymers by Differential Scanning
Calorimetry
Raman Spectroscopy
Identification marks
Physical Testing/Chemical Testing
© SPEX CertiPrep, Inc. 2012Polymer Identification
Code Abbreviation Plastic Examples
1 PET or PETE Polyethylene Terephthalate Soft drink bottles
2 HDPE High Density Polyethylene Milk jugs, bottles, toys
3 PVC Polyvinyl Chloride Pipe, Shower curtains, toys
4 LDPE Low density Polyethylene Shopping bags, toys
5 PP Polypropylene Food containers, dishware
6 PS Polystyrene Food containers, toys
7 Other Polycarbonate Drink containers, toys
Extruded, molded objects
9 ABS Acrylonitrile butadiene styrene
(Legos)
© SPEX CertiPrep, Inc. 2012Polymer Characteristics
Density Flame Hex Chex Tol Ace DCM THF Melting Point (oC)
Blue with yellow,
0.85-0.94 I I I I S SW 130-171
PP slight grime
Blue with yellow,
0.92-0.98 I I I I I I 105-130
PE slight grime
Blue with yellow,
0.91-0.94 I I I I I I 105-115
LDPE slight grime
Blue with yellow,
0.94-0.97 I I I I I I 120-130
HDPE slight grime
Blue with yellow,
1.04* Small float I I S S S S >80
ABS slight grime
PS 1.05-1.07 Yellow S S S S S S
1.16-1.45
100-260* additives
(Rigid = 1.3-1.45) Green I I SW SW S S
used
PVC (Soft = 1.16-1.3)
Glass state: 150
1.2-1.22 Yellow orange I S S S S S
PC Melt state: 267
I= Insoluble S= Soluble SW= Swell
© SPEX CertiPrep, Inc. 2012Toy Identification Flowchart • Blue Squares = Density Tests • Pink Diamond = Solubility Tests • Green Square = Tentative ID • Red Circle = Final ID • Yellow Triangle = Flame Test © SPEX CertiPrep, Inc. 2012
Toy Identification Flowchart
© SPEX CertiPrep, Inc. 2012Toy Identification Flowchart
© SPEX CertiPrep, Inc. 2012Toy Identification Flowchart
© SPEX CertiPrep, Inc. 2012Toy Identification Flowchart
© SPEX CertiPrep, Inc. 2012Sample Identifications
# of
Type Samples
LDPE
PVC 17
22
LDPE
PVC 17
22
HDPE 6
PC 7
PP 2
ABS 1
Silicone 1
Cloth 1
© SPEX CertiPrep, Inc. 2012HDPE Toys
Plastic Figures
• Police
• Military
• Fireman
Toy Car Parts
• Black Base
• Black Wheel
• Silver parts
© SPEX CertiPrep, Inc. 2012PVC Toys
• Snake figures • Three cartoon figures
• Three dinosaur figures • Two shark figures
© SPEX CertiPrep, Inc. 2012PVC Toys With Possible Oral Contact
• Rubber Duck • Fashion Doll • Snorkel
• Lion • Party Teeth
© SPEX CertiPrep, Inc. 2012Polymer Identification & Analysis
Solvent solubility can change extraction method
Some methods are polymer specific-
• CPSC Method- PVC polymer precipitation method
Different concerns for additives or contaminants in each polymer can
possibly change extraction goals.
Plastic Dangers
Polyethylene Terephthalate Acetaldehyde, antimony
High Density Polyethylene Small amounts of additives
Polyvinyl Chloride Phthalates, BPA, Heavy Metals
Low Density Polyethylene Small amounts of additives
Polypropylene Olemide, Quaternary biocides
Polystyrene Styrene, flammability risk
Polycarbonate BPA
Acrylonitrile butadiene styrene Hydrogen cyanide combustion product
© SPEX CertiPrep, Inc. 2012Sample Extraction: CPSC
© SPEX CertiPrep, Inc. 2012CPSC Wet Extraction Method: PVC
© SPEX CertiPrep, Inc. 2012CPSC Wet Extraction Method: PVC
© SPEX CertiPrep, Inc. 2012CPSC Wet Extraction Method: PVC
For 0.05 g = 15 mL solvent minimum
• PVC Toy samples don’t always
precipitate with 15 mL
• Increased solvent dilutes sample
At the CPSC limit (0.1% or 1000 ug/g)
• Straight GC injection = 3 ppm
• Diluted per method = 0.7 ppm
Must use SIM
• Miss other additives
• Misidentify other additives
as phthalates
• Miss low level phthalates
or BPA
What is the extraction efficiency of the
method?
© SPEX CertiPrep, Inc. 2012CPSC Wet Extraction Method: PVC
SPEX CertiPrep CRM-PE001:
Polyethylene Matrix
CPSC Wet Method
• Recovery Wet Method for %RSD
PVC = 50% Dimethyl phthalate 35.09
Diethyl phthalate 36.96
New CRM developed for PVC
Di-n-butyl phthalate 48.42
• Recovery for CPSC Method Butyl benzyl phthalate 57.72
= 83 – 94% Bis(2-ethylhexyl)phthalate 58.05
• Poor Reproducibility Di-n-octyl phthalate 58.24
• GC Contamination Diisononyl phthalate 50.97
Diisodecyl phthalate 60.69
© SPEX CertiPrep, Inc. 2012Comparison of CPSC Wet Method
vs. Microwave Extraction
CPSC Wet method Microwave method
• Large amounts of solvent • 10 – 15 mL of solvent for up to 1
• Less concentration on GCMS g of sample
system: miss some additives • Allows high enough concentration
• Interference of polymers with of small phthalates to see on
GCMS operation GCMS
• Poor reproducibility • Dilution possible for higher
concentration phthalates
• Time consuming
• Little interference/carryover seen
on GCMS
• Great reproducibility
• Fast, multiple samples processed
at once
© SPEX CertiPrep, Inc. 2012Comparison of CPSC Wet Method
vs. Microwave Extraction
Optimized Microwave Method CPSC Wet Method
%RSD %RSD
Dimethyl phthalate 2.48 35.09
Diethyl phthalate 0.72 36.96
Di-n-butyl phthalate 0.70 48.42
Butyl benzyl phthalate 2.26 57.72
Bis(2-ethylhexyl)phthalate 1.02 58.05
Di-n-octyl phthalate 1.29 58.24
Diisononyl phthalate 0.36 50.97
Diisodecyl phthalate 0.94 60.69
© SPEX CertiPrep, Inc. 2012© SPEX CertiPrep, Inc. 2012
PVC Toys: DEHP
Total DEHP in each toy sample
30000.00
25000.00
20000.00
US limit 1000 ppm
DEHP (µg/g)
15000.00
10000.00
5000.00
0.00
Toy Sample
© SPEX CertiPrep, Inc. 2012PVC Toys: Total Phthalates
Total Concentration of Six Restricted Phthalates in Each Toy Sample
1000000.00
EU/Japan limit
100000.00 US limit
Total of 6 restricted phthalates (µg/g)
10000.00
1000.00
100.00
10.00
1.00
Toy Sample
© SPEX CertiPrep, Inc. 2012Results: BPA
Concentration of BPA in Selected Toy Samples
1400.00
1200.00
1000.00
Conc of BPA (µg/g)
800.00
600.00
400.00
200.00
0.00
Triceratops Duck Doll Head
Toy Sample © SPEX CertiPrep, Inc. 2012In Summary
Toys Preparation for Testing includes:
– Separation into parts
– Removal of stickers and/or paint
– Samples: powder or piecesIn Summary
Extraction Concerns
– CPSC wet method = PVC only – does not work for all
polymers
• PE tested with this method = 50% recovery
• Extraction efficiency can be checked with QC CRM
• Limitations/Problems
– Polymer may not fully precipitate
» problems with GC/MS reproducibility (high RSD)
– Large amounts of solvent and dilutions
» Reduces ability to see lower level phthalates & BPA
» SIM = cannot see other additives which might be
mistaken as phthalates
© SPEX CertiPrep, Inc. 2012In Summary
Phthalates in PVC
– Most prevalent phthalate = DEHP
– High concentrations in majority of PVC samples
• Excess of CPSC
– Two oral contact samples 10,000 – 30,000 ug/g DEHP
– BPA found in 3 PVC samples
Part II
– Extraction optimization
– Analysis
– Detailed Results
© SPEX CertiPrep, Inc. 2012Standards Used in This Study
Phthalate & BPA Standards from SPEX CertiPrep:
S-509: Bisphenol A Standard
CRM-PE001: PE QC Standard
CRM-PEBLK: PE Blank
CRM-PVC001: PVC QC Standard
CRM-PVCBLK: PVC Blank
SS-CRM-PVC001: Phthalate Standard
CLPS-1: Internal Standards
© SPEX CertiPrep, Inc. 2012Questions?
Additional questions can be sent to
CRMSales@spex.com
© SPEX CertiPrep, Inc. 2012New Products
Full line of 1 ppm ICP-MS Trace Metals in Natural Wine
Single Element Standards Matrix Standards
– Red: TM-WINE-R1A
– White: TM-WINE-W1A
© SPEX CertiPrep, Inc. 2012Win a Keurig Personal Coffee Maker!
Included in the follow up email blast today will be a link to a
general survey
Complete the survey and include your contact information
and you will be entered into a drawing for a FREE Keurig!
© SPEX CertiPrep, Inc. 2012Thank You!
Contact Us!
Pat Atkins
Matt Snyder
CRMSales@spex.com
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