Part 1: The Sample Preparation of Imported Plastic Toys ... · • Commercial use in 1920’s Uses...

© SPEX CertiPrep, Inc. 2012

1

Patricia AtkinsSPEX CertiPrep

Part 1: The Sample Preparation of Imported Plastic Toys for the Analysis of BPA & Phthalates


Housekeeping

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The webinar is being recorded and will be posted to our YouTube account

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

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Part 1: Sample Preparation

Introduction & Background on Plastics

Plastic Identification

Sample Preparation Techniques and Methods

Overview of the CPSC PVC method

Snapshot of findings


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


In the News


The Best Reason to Study Phthalates


Background• Produced since late 1800’s• Commercial use in 1920’s

Background• Produced since late 1800’s• Commercial use in 1920’s

Uses• Plastic compounds

(10-60% by wt)• Binders• Coatings• Fragrances and pigments

Uses• Plastic compounds

(10-60% by wt)• Binders• Coatings• Fragrances and pigments

Health Effects• Residue is widespread• Variety of disorders:

asthma, reproductive• Endocrine disruptor

Health Effects• Residue is widespread• Variety of disorders:

asthma, reproductive• Endocrine disruptor

Response• US ban children’s toys

2009• Mexico, the EU, and Japan

restricted or banned the use of phthalates in children’s toys

Response• US ban children’s toys

2009• Mexico, the EU, and Japan

restricted or banned the use of phthalates in children’s toys

Phthalates


Common Phthalates

Name Acronym Structural formula CAS No.Dimethyl phthalate DMP C6H4(COOCH3)2 131-11-3Diethyl phthalate DEP C6H4(COOC2H5)2 84-66-2Diallyl phthalate DAP C6H4(COOCH2CH=CH2)2 131-17-9

Di-n-propyl phthalate DPP C6H4[COO(CH2)2CH3]2 131-16-8Di-n-butyl phthalate DBP C6H4[COO(CH2)3CH3]2 84-74-2Diisobutyl phthalate DIBP C6H4[COOCH2CH(CH3)2]2 84-69-5

Butyl cyclohexyl phthalate BCP CH3(CH2)3OOCC6H4COOC6H11 84-64-0Di-n-pentyl phthalate DNPP C6H4[COO(CH2)4CH3]2 131-18-0

Dicyclohexyl phthalate DCP C6H4[COOC6H11]2 84-61-7Butyl benzyl phthalate BBP CH3(CH2)3OOCC6H4COOCH2C6H5 85-68-7Di-n-hexyl phthalate DNHP C6H4[COO(CH2)5CH3]2 84-75-3Butyl 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]2 117-84-0Diisodecyl 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


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

6 Restricted Phthalates


Regulations & Banned Phthalates

DEHP DBP BBP DINP DIDP DNOP

US CPSIA CPSC-CH-C1001-09.03

0.1% individual (All toys & Childcare)



0.1% individual

(Oral Contact)

0.1% individual

(Oral Contact)

0.1% individual

(Oral Contact)

EU EC Directive 2005/84/EC 0.1% combined (All toys)

0.1% combined(Toys with Oral Contact)

Japan ST Standard Part 3 / Food Sanitation Law

0.1% combined(All toys)

0.1% combined (Toys with Oral Contact)


Bisphenol A

Background• 3.7 million metric

tons/yr• Reported in 1891

Uses• Polymers• Coatings and epoxy

resins

Health Effects• Suggested estrogenic

effects in the 1930’s• Endocrine disruptor

Regulations• The EPA guideline - 50

µg/kg/day• As low as 0.025

µg/kg/day can have adverse effects


Regulations

Area Scope of BPA Ban Requirement

US Various childcare products No National Ban; State by State

EU PC baby bottles Banned

CanadaPC baby bottles Banned

BPA deemed toxic Action


Testing 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


Toy 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


Sample Preparation: Separation

26 Toys >65 samples Stickers were removed Paint was not removed

• Metals testing = remove paint when possible


Sample 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


Grinding Tips

General Program 2.5 grams of plastic Pieces cut to <5 mm Run 8 vials at a time

• 4 vials with Multi-Vial adapter in each sample chamber

Program Precool = 20 minutes Grind for 5 cycles (2 min/cycle) Each cycle = 2 min. cooling Impact rate= 16 impacts/second

• Difficult plastics = additional precooling


Sample Preparation: GrindingCryogenic grinding allows for a fine analytical powder not possible with room temperature grinding.


Particle size & Extraction

Decreased particle size > surface area

CPSC = <2 mm or ground samples

Experiment – PVC material > 5mm 5 mm Random 2-5 mm 2 mm Ground Samples

Samples extracted using microwave extraction

Samples extracted by wet method


Grinding and Extraction EfficiencyMicrowave Extraction

5 mm 2 mm Powder


Grinding and Extraction EfficiencyCPSC Wet Method

2 mm Powder


Sample 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



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



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




Methods 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


Polymer Identification

Code Abbreviation Plastic Examples

PET or PETE Polyethylene Terephthalate Soft drink bottles

HDPE High Density Polyethylene Milk jugs, bottles, toys

PVC Polyvinyl Chloride Pipe, Shower curtains, toys

LDPE Low density Polyethylene Shopping bags, toys

PP Polypropylene Food containers, dishware

PS Polystyrene Food containers, toys

Other Polycarbonate Drink containers, toys

ABS Acrylonitrile butadiene styrene Extruded, molded objects (Legos)

1

2

3

4

5

6

7

9


Polymer Characteristics

Density Flame Hex Chex Tol Ace DCM THF Melting Point (oC)

PP0.85-0.94 Blue with yellow,

slight grime I I I I S SW 130-171

PE0.92-0.98 Blue with yellow,

slight grime I I I I I I 105-130

LDPE0.91-0.94 Blue with yellow,


HDPE0.94-0.97 Blue with yellow,


ABS1.04* Small float Blue with yellow,

slight grime I I S S S S >80

PS 1.05-1.07 Yellow S S S S S S

PVC

1.16-1.45 (Rigid = 1.3-1.45) (Soft = 1.16-1.3)

Green I I SW SW S S 100-260* additives used

PC1.2-1.22 Yellow orange I S S S S S Glass state: 150

Melt state: 267

I= Insoluble S= Soluble SW= Swell


Toy Identification Flowchart

• Blue Squares = Density Tests• Pink Diamond = Solubility Tests• Green Square = Tentative ID• Red Circle = Final ID• Yellow Triangle = Flame Test










Sample Identifications

Type# of

Samples

PVC 17

LDPE 22

HDPE 6

PC 7

PP 2

ABS 1

Silicone 1

Cloth 1

Type# of

Samples

LDPE 22

PVC 17

HDPE 6

PC 7

PP 2

ABS 1

Silicone 1

Cloth 1


HDPE Toys

Plastic Figures• Police• Military• Fireman

Toy Car Parts• Black Base• Black Wheel• Silver parts


PVC Toys

• Snake figures • Three cartoon figures

• Three dinosaur figures • Two shark figures


PVC Toys With Possible Oral Contact

• Rubber Duck • Snorkel

• Lion

• Fashion Doll

• Party Teeth


Polymer Identification & Analysis

Plastic DangersPolyethylene 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

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.


Sample Extraction: CPSC


CPSC 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 CRM-PE001: Polyethylene Matrix• Recovery Wet Method for

PVC = 50% New CRM developed for PVC

• Recovery for CPSC Method = 83 – 94%

• Poor Reproducibility• GC Contamination

CPSC Wet Method%RSD

Dimethyl phthalate 35.09

Diethyl phthalate 36.96

Di-n-butyl phthalate 48.42

Butyl benzyl phthalate 57.72

Bis(2-ethylhexyl)phthalate 58.05

Di-n-octyl phthalate 58.24

Diisononyl phthalate 50.97

Diisodecyl phthalate 60.69



Comparison of CPSC Wet Method vs. Microwave Extraction

CPSC Wet method• Large amounts of solvent• Less concentration on GCMS

system: miss some additives• Interference of polymers with

GCMS operation• Poor reproducibility• Time consuming

Microwave method• 10 – 15 mL of solvent for up to 1

g of sample• Allows high enough concentration

of small phthalates to see on GCMS

• Dilution possible for higher concentration phthalates

• Little interference/carryover seen on GCMS

• Great reproducibility• Fast, multiple samples processed

at once


Optimized Microwave Method CPSC Wet Method%RSD %RSD

Dimethyl phthalate 2.48 35.09Diethyl phthalate 0.72 36.96Di-n-butyl phthalate 0.70 48.42Butyl benzyl phthalate 2.26 57.72Bis(2-ethylhexyl)phthalate 1.02 58.05Di-n-octyl phthalate 1.29 58.24Diisononyl phthalate 0.36 50.97Diisodecyl phthalate 0.94 60.69

Comparison of CPSC Wet Method vs. Microwave Extraction



PVC Toys: DEHP

0.00

5000.00

10000.00

15000.00

20000.00

25000.00

30000.00

Total DEHP in each toy sample

US limit 1000 ppm

DE

HP

(µg/

g)

Toy Sample


PVC Toys: Total Phthalates

1.00

10.00

100.00

1000.00

10000.00

100000.00

1000000.00

Total Concentration of Six Restricted Phthalates in Each Toy Sample

Tota

l of 6

rest

ricte

d ph

thal

ates

(µg/

g)

Toy Sample

US limit

EU/Japan limit


Results: BPA

0.00

200.00

400.00

600.00

800.00

1000.00

1200.00

1400.00

Triceratops Duck Doll Head

Concentration of BPA in Selected Toy Samples

Toy Sample

Con

cof

BPA

(µg/

g)


In Summary

Toys Preparation for Testing includes:

– Separation into parts

– Removal of stickers and/or paint

– Samples: powder or pieces <2 mm

• Powders increase surface area and extraction materials

• Grinding works best under cryogenic conditions

• Blank CRM materials monitor potential process contamination

Identification of plastics

– Helps refine extraction

• Multiple ways to ID: markings, IR, Raman, DSC, TGA and Physical / Chemical Testing


In 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


In 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


Standards 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


Questions?

Additional questions can be sent to [email protected]


New Products

Full line of 1 ppm ICP-MS Single Element Standards

Trace Metals in Natural Wine Matrix Standards– Red: TM-WINE-R1A

– White: TM-WINE-W1A


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Complete the survey and include your contact information and you will be entered into a drawing for a FREE Keurig!


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Part 1: The Sample Preparation of Imported Plastic Toys ... · • Commercial use in 1920’s Uses...

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