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Survey and release of chemical substances in "slimy" toys

3 Analysis results

• 3.1 FTIR screening
  • 3.1.1 Equipment and methods
  • 3.1.2 Results from the FTIR screening
  • 3.1.3 Summary of the FTIR screening
• 3.2 Quantitative determination of phthalate by GC-MS
  • 3.2.1 Analysis method
  • 3.2.2 Analysis results for phthalates
  • 3.2.3 Summary
• 3.3 Headspace analysis results from screening
  • 3.3.1 Analysis method
  • 3.3.2 Results from the headspace analysis
  • 3.3.3 Summary of the headspace analyses
• 3.4 GC-MS Analysis results from screening
  • 3.4.1 Analysis method
  • 3.4.2 Results from the GC-MS screening analysis
  • 3.4.3 Summary of the GC-MS screening analysis
• 3.5 ICP analysis results from screening
  • 3.5.1 Analysis method
  • 3.5.2 Results from the ICP-MS screening
  • 3.5.3 Summary of the ICP-MS screening
• 3.6 Boric acid determination by ICP-AES
  • 3.6.1 Analysis method
  • 3.6.2 Results from the boric acid determination by ICP-AES
  • 3.6.3 Summary of boric acid determination by ICP-AES

3.1 FTIR screening

3.1.1 Equipment and methods

For the FTIR analyses, a Nicolet Magna 550 FTIR equipment with installed optical bench has been used. The bench gathers the IR pencil of rays to approx. 2 mm in diameter, supplied with FTIR microscope with diamant cell.

The specimens have been cut out from the examined samples by means of a scalpel. In the case of jelly materials, the diamond cell has been used, as it presses all the materials to a thin film of approx. 10 µm. At the measurements, the pencil of rays is approx. 100 µm. In the case of thermoplastic materials, the sample preparation has consisted of hot-pressing of approx. 2 to 5 mg of material for film with a thickness of 10 to 20 µm. This film has been analysed by screening.

In the case of extraction, methylene chloride has been used. After drying, the evaporation residue has been ground with potassium bromide and finally pressing of a tablet, on which the analysis has been done. A sample amount of approx. 1 mg is used.

Interpretation of the FTIR spectra has been done partly based on experience and partly according to our reference library, among others “Hummel Polymer and Additives” and through external search on “FTIRsearch.com”.

In addition to the actual material analyses, we have looked for various additives.

In connection with additives, which might be added in relatively small amounts, only in the cases where over approx. 0.1 weight% is added and that the additive has strong absorption bands outside the absorptions from the polymer, it will be detectable.

3.1.2 Results from the FTIR screening

The FTIR screening was carried out as follows: on all purchased “slimy toys” FTIR analysis has been carried out on all types of material detected on each product. Results are stated in Table 3.1 and in Enclosure B.

Table 3.1 Results from the FTIR screening

3.1.3 Summary of the FTIR screening

At the analyses two types of “slime” are detected, partly an aqueous type, hydro gels, and partly a type based on hydrocarbons with a small content of styrene.

At the aqueous slime, content of glycerol and acrylate has been detected, and - in some cases - material which we have not been able to identify by FTIR.

In a number of cases, parabenes have been added. Generally, in case of the slime products made of hydrocarbons, we cannot detect other components.

3.2 Quantitative determination of phthalate by GC-MS

3.2.1 Analysis method

Analyses programme for phthalates

Determination of content of selected phthalates

A weighed out sample amount was extracted with dichloromethane added deuterium-marked internal standards in the form of DEHPd4 and BBP-d4 by ultrasound for 2 hours. The extract was analysed by gas chromatography combined with mass spectrometer detector (GC-MS) in scan mode.

The components were identified on the basis of the actual retention times and mass spectra.

Calibration curves were made for each of the selected phthalates.

Recommended limits of detection (LOD):

Single components: 20 µg/g (0.002% m/m)

DINP and DIDP: 50 µg/g (0.005 % m/m)

3.2.2 Analysis results for phthalates

3.2.3 Summary

The quantitative determination of phthalates shows that one of the products exceeded the threshold limit value of 0.05 weight%.

3.3 Headspace analysis results from screening

3.3.1 Analysis method

Qualitative analysis of the degassing components by headspace analysis, for the purpose of identification.

After the receipt, the samples were put in an airproof rilsan bag.

Glass tubes with a fixed adsorbent (Tenax tube) were placed next to them in the rilsan bag. The Tenax tubes were subsequently analysed by thermal desorption combined with gas chromatography with mass spectrometer detector (ATD/GC-MS).

A Perkin-Elmer TurboMass Spectrometer with Perkin-Elmer ATD 400 was used.

The components were identified by comparing the respective mass spectra with mass spectra from NIST library.

3.3.2 Results from the headspace analysis

Results are stated in Table 3.2 and Enclosure C.

For each piece of slimy toy the identified components in the degassing have been listed, and the relative amount of each component is stated as a percentage part of the total degassing from the sample (total VOC content).

The stated percentage share of total VOC-content has been calculated on the assumption that all detected components have the same response for the same amount.

Click her to see Table 3.2

3.3.3 Summary of the headspace analyses

At the headspace analyses of 14 slimy toys (of which a few were analysed on exterior part and interior liquid part, totally 20 analyses), we found 61 identified single substances and various groups of substances consisting of various aliphatic and aromatic hydrocarbons, which are stated in groups characterised by the number of carbon-atoms, and finally 6 compounds, which could not be identified.

The majority (80%) of the examined products are main components in the degassing aliphatic hydrocarbons, primarily C10-C14 and aromatic hydrocarbons such as toluene, xylenes and trimethyl benzenes. Two of these products furthermore contain more volatile aliphatic hydrocarbons such as C7-C8.

In two of the products (TO-01 and TO-02) cyclohexanone constitutes 63% and 30% respectively of the total degassing. Other samples are characterised by the content of alcohols. It should be noticed that a few of the products contain traces of D-limonene (allergenic odorant).

3.4 GC-MS Analysis results from screening

3.4.1 Analysis method

Screening of extracts from artificial saliva and sweat by GC-MS.

Sample preparation

1-2 g sample - accurately weighed out - was in a Red Cap bottle added 20 ml artificial saliva solution or artificial sweat solution and extracted in an end-over-end shaker for 4 hours in heating chamber at 40C. The extract was moved to a 20 ml calibrated flask, filled until 20 ml with saliva- or sweat solution and added deuterium-marked internal standards in the form of benzene, toluene, p-xylene and naphthalene, together with 1 ml pentane. The calibrated flasks were shaken for 10 min, after which the pentane phase was isolated.

Analysis

The pentane extracts were analysed by GC-MS in scan mode.

Apparatus

An HP gas chromatograph 5890 with an HP mass spectrometer 5972 was used.

3.4.2 Results from the GC-MS screening analysis

Results are stated in Table 3.3 and in Enclosure D.

3.4.3 Summary of the GC-MS screening analysis

At the migration analyses of the 14 slimy toys (of which a few were analysed on exterior part and interior part, totally 17 analyses) we found 22 identified single substances and various groups of substances consisting of various aliphatic and aromatic hydrocarbons, which are stated in groups characterised by the number of carbon-atoms, and finally a group of 6 compounds, which could not be identified, but they were all fatty acids.

Click her to see Table 3.3

3.5 ICP analysis results from screening

3.5.1 Analysis method

Sample preparation

Approx. 500 mg sample - accurately weighed out - was prepared by means of microwave induced heating in a PFA autoclave with 20 ml 7 M HNO3 (sub boiling quality). The resulting solution was filtered and consequently diluted to 50 ml with demineralised water (Milli- Q Plus).

Repeat preparation was carried out.

Blank tests were correspondingly prepared.

Standard

Standards and control tests were made based on a Merck multi-element standard solution VI by diluting with 2.8 M HNO3.

The internal standard mixture was made based on Perkin-Elmer single-element standards of Ge, Rh and Re by diluting with 0.14 M HNO3.

Apparatus

A Perkin-Elmer Sciex Elan 6100 DRC Plus ICP mass spectrometer with FIAS 400 flow injection system and autosampler AS 93 Plus was used.

Screening analysis

The prepared samples, added “on-line” germanium, rhodium and rhenium as internal standards, were screened for the content of trace elements through inductive-coupled-plasma mass spectrometry (ICP-MS) using the expert programme TotalQuantII, which - on the basis of an instrument response curve for the elemental substances from mass 6 (Li) to mass 238 (U) - quantifies the content. The instrument response curve was updated by means of a multi-element standard containing Li, Be, B, Na, Mg, Al, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Mo, Ag, Cd, Te, Ba, Tl, Pb, Bi and U, which covers all of the mass area. Elemental substances like Br, C, Cl, F, N, O, P, S and Si are not quantified because of interferences.

3.5.2 Results from the ICP-MS screening

Results are stated in Enclosure E.

3.5.3 Summary of the ICP-MS screening

The screening analyses show a considerable content of boron in 3 of the samples (DK-01, TO-01 and TO-02). Boron might be added as a preservative in the form of boric acid or sodium borate, as a sodium content has also been measured. However, there might be other sodium sources, e.g. sodium benzoate, which is also a preservative. Content of elements such as aluminium, calcium, potassium, magnesium and zinc, detected in most of the samples, presumably derives from fillers or auxiliary constituents used in the production of the products. Furthermore, the detection of traces from a few heavy metals in some of the samples is supposed to derive from contaminations from fillers and possibly from production equipment and production conditions.

Nickel is classified: Carc3;R40 R43. Most nickel compounds are classified because of the allergenic property with R43, May cause sensitization by skin contact.

A number of nickel compounds are either known to have a cancer-causing effect or suspected to have a cancer-causing effect, like e.g. nickel carbonate or nickel sulphate.

Furthermore, most nickel compounds are classified as harmful to the environment with R50/53, very toxic to aquatic organisms and not degradable.

Nickel was detected in the screening in 2 products (TO-01 and A-01), but only in small amounts.

3.6 Determination of Boron by ICP-AES

3.6.1 Analysis method

Analysis

The solutions prepared under point 3.5.1 were analysed quantitatively for the content of boron through inductive-coupled-plasma atomic emission spectrometry (ICP-AES).

Standards

Boron standards were made from a Perkin-Elmer stock solution through dilution with 2.8 M HNO3.

Apparatus

A Perkin-Elmer Optima 3300 DV inductive-coupled-plasma atomic emission spectrometry with autosampler AS-90 plus was used.

3.6.2 Results from the determination of boron by ICP-AES

Results are stated in Enclosure F and Table 3.4 below.

Table 3.4 Result of quantitative analysis of boron

%RSD indicates the percentage relative standard deviation based on repeat determination

”-” indicates less than the limit of detection listed in the rightmost column

DL indicates the limit of detection

3.6.3 Summary of the determination of boron by ICP-AES

The quantitative determination of boron by ICP-AES confirms results achieved by the ICP-MS screening of all samples. The higher content (25-45%) in the samples DK-01, TO-01 and TO-02 determined by ICP-AES compared with the ICP-MS screening must be seen based on the fact that the concentrations in the measuring solutions by ICP-MS screening of these samples are far above the calibration area.

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Version 1.0 March 2006, © Danish Environmental Protection Agency