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

Transcription

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

2 Housekeeping Everyone will receive a copy of the presentation slides 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 Stick around after the Q & A session for details on your chance to win a Keurig Coffee Maker!

3 Part 1: Sample Preparation Introduction & Background on Plastics Plastic Identification Sample Preparation Techniques and Methods Overview of the CPSC PVC method Snapshot of findings

4 Part 2: Sample Extraction & Analysis Offered June 7 th at 10AM and 2PM with registration next week Details about CPSC method Extraction methods development Microwave methods optimization Comparison to CPSC PVC method GCMS Analysis Detailed Findings

5 In the News

6 The Best Reason to Study Phthalates

7 Phthalates Background Produced since late 1800 s Commercial use in 1920 s Uses Plastic compounds (10-60% by wt) Binders Coatings Fragrances and pigments 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

8 Common Phthalates Name Acronym Structural formula CAS No. Dimethyl phthalate DMP C 6 H 4 (COOCH 3 ) Diethyl phthalate DEP C 6 H 4 (COOC 2 H 5 ) Diallyl phthalate DAP C 6 H 4 (COOCH 2 CH=CH 2 ) Di-n-propyl phthalate DPP C 6 H 4 [COO(CH 2 ) 2 CH 3 ] Di-n-butyl phthalate DBP C 6 H 4 [COO(CH 2 ) 3 CH 3 ] Diisobutyl phthalate DIBP C 6 H 4 [COOCH 2 CH(CH 3 ) 2 ] Butyl cyclohexyl phthalate BCP CH 3 (CH 2 ) 3 OOCC 6 H 4 COOC 6 H Di-n-pentyl phthalate DNPP C 6 H 4 [COO(CH 2 ) 4 CH 3 ] Dicyclohexyl phthalate DCP C 6 H 4 [COOC 6 H 11 ] Butyl benzyl phthalate BBP CH 3 (CH 2 ) 3 OOCC 6 H 4 COOCH 2 C 6 H Di-n-hexyl phthalate DNHP C 6 H 4 [COO(CH 2 ) 5 CH 3 ] Butyl decyl phthalate BDP CH 3 (CH 2 ) 3 OOCC 6 H 4 COO(CH 2 ) 9 CH Di(2-ethylhexyl) phthalate DEHP C 6 H 4 [COOCH 2 CH(C 2 H 5 )(CH 2 ) 3 CH 3 ] Di(n-octyl) phthalate DNOP C 6 H 4 [COO(CH 2 ) 7 CH 3 ] Diisodecyl phthalate DIDP C6H4[COO(CH2)7CH(CH3)2] n-octyl n-decyl phthalate ODP CH 3 (CH 2 ) 7 OOCC 6 H 4 COO(CH 2 ) 9 CH Diisononyl phthalate DINP C 6 H 4 [COO(CH 2 ) 6 CH(CH 3 ) 2 ]

9 6 Restricted Phthalates Name Acronym Structural formula CAS No. Di-n-butyl phthalate DBP C 6 H 4 [COO(CH 2 ) 3 CH 3 ] Butyl benzyl phthalate BBP CH 3 (CH 2 ) 3 OOCC 6 H 4 COOCH 2 C 6 H Di(2-ethylhexyl) phthalate DEHP C 6 H 4 [COOCH 2 CH(C 2 H 5 )(CH 2 ) 3 CH 3 ] Di(n-octyl) phthalate DNOP C 6 H 4 [COO(CH 2 ) 7 CH 3 ] Diisodecyl phthalate DIDP C6H4[COO(CH2)7CH(CH3)2] Diisononyl phthalate DINP C 6 H 4 [COO(CH 2 ) 6 CH(CH 3 ) 2 ]

10 Regulations & Banned Phthalates DEHP DBP BBP DINP DIDP DNOP US CPSIA CPSC-CH-C % individual (All toys & Childcare) 0.1% individual (All toys & Childcare) 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)

11 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 µg/kg/day can have adverse effects

12 Regulations Area Scope of BPA Ban Requirement US Various childcare products No National Ban; State by State EU PC baby bottles Banned Canada PC baby bottles BPA deemed toxic Banned Action

13 Testing Method for Phthalates CPSC-CH-C Standard Operating Procedure for Determination of Phthalates (Children s Toys & Childcare Articles) Measurement of 6 Restricted Phthalates Outlines: Sample Preparation Extraction Analysis

14 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

15 Sample Preparation: Separation 26 Toys >65 samples Stickers were removed Paint was not removed Metals testing = remove paint when possible

16 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

17 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 SPEX CertiPrep, Inc. 2012

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

19 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

20 Grinding and Extraction Efficiency Microwave Extraction 5 mm 2 mm Powder

21 Grinding and Extraction Efficiency CPSC Wet Method 2 mm Powder

22 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

23 Sample 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

24 Sample 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 ( o C) PP PE LDPE HDPE ABS >80 PC Glass state: 150 Melt state: 267 PVC * additives used

25 Sample Preparation: Grinding Tips

26 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

27 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 6 7 PS Polystyrene Food containers, toys Other Polycarbonate Drink containers, toys 9 ABS Acrylonitrile butadiene styrene Extruded, molded objects (Legos)

28 Polymer Characteristics PP PE LDPE HDPE Density Flame Hex Chex Tol Ace DCM THF Melting Point ( o C) Blue with yellow, I I I I S SW slight grime Blue with yellow, slight grime Blue with yellow, slight grime Blue with yellow, slight grime I I I I I I I I I I I I I I I I I I Blue with yellow, 1.04* Small float I I S S S S >80 ABS slight grime PS Yellow S S S S S S PVC PC (Rigid = ) (Soft = ) Green I I SW SW S S Yellow orange I S S S S S * additives used Glass state: 150 Melt state: 267 I= Insoluble S= Soluble SW= Swell

29 Toy Identification Flowchart Blue Squares = Density Tests Pink Diamond = Solubility Tests Green Square = Tentative ID Red Circle = Final ID Yellow Triangle = Flame Test

30 Toy Identification Flowchart

31 Toy Identification Flowchart

32 Toy Identification Flowchart

33 Toy Identification Flowchart

34 Sample Identifications Type # of Samples LDPE PVC LDPE PVC HDPE 6 PC 7 PP 2 ABS 1 Silicone 1 Cloth 1

35 HDPE Toys Plastic Figures Police Military Fireman Toy Car Parts Black Base Black Wheel Silver parts

36 PVC Toys Snake figures Three cartoon figures Three dinosaur figures Two shark figures

37 PVC Toys With Possible Oral Contact Rubber Duck Fashion Doll Snorkel Lion Party Teeth

38 Polymer 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 Polyethylene Terephthalate High Density Polyethylene Polyvinyl Chloride Low Density Polyethylene Polypropylene Polystyrene Polycarbonate Dangers Acetaldehyde, antimony Small amounts of additives Phthalates, BPA, Heavy Metals Small amounts of additives Olemide, Quaternary biocides Styrene, flammability risk BPA Acrylonitrile butadiene styrene Hydrogen cyanide combustion product

39 Sample Extraction: CPSC

40 CPSC Wet Extraction Method: PVC

41 CPSC Wet Extraction Method: PVC

42 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?

43 CPSC Wet Extraction Method: PVC 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 Diethyl phthalate Di-n-butyl phthalate Butyl benzyl phthalate Bis(2-ethylhexyl)phthalate Di-n-octyl phthalate Diisononyl phthalate Diisodecyl phthalate 60.69

44 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 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

45 Comparison of CPSC Wet Method vs. Microwave Extraction Optimized Microwave Method CPSC Wet Method %RSD %RSD Dimethyl phthalate Diethyl phthalate Di-n-butyl phthalate Butyl benzyl phthalate Bis(2-ethylhexyl)phthalate Di-n-octyl phthalate Diisononyl phthalate Diisodecyl phthalate

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47 PVC Toys: DEHP Total DEHP in each toy sample US limit 1000 ppm DEHP (µg/g) Toy Sample

48 PVC Toys: Total Phthalates Total Concentration of Six Restricted Phthalates in Each Toy Sample EU/Japan limit Total of 6 restricted phthalates (µg/g) US limit Toy Sample

49 Results: BPA Concentration of BPA in Selected Toy Samples Conc of BPA (µg/g) Triceratops Duck Doll Head Toy Sample

50 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

51 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

52 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

53 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

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55 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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