| Front page | | Contents | | Previous | | Next |

Survey, emission and health assessment of chemical substances in baby products

2 Survey of content of chemical substances – chemical analyses

• 2.1 Analysis programme
  • 2.1.1 Foam materials
  • 2.1.2 Textiles
  • 2.1.3 Polymer materials
  • 2.1.4 Polystyrene pellets
  • 2.1.5 Summary of performed analyses
• 2.2 Methods
  • 2.2.1 Analysis for content of azo-colourants
  • 2.2.2 Analysis for content of disperse colourants
  • 2.2.3 Analysis of the content of selected organic tin compounds
  • 2.2.4 Analysis of the content of selected organic phosphorous compounds
  • 2.2.5 Analysis of content of chlorinated benzenes and toluenes
  • 2.2.6 Analysis for content of chlorinated phenols and OPP
  • 2.2.7 Analysis for content of selected phthalates
  • 2.2.8 Analysis for content of formaldehyde
  • 2.2.9 Screening analyse by GC-MS
  • 2.2.10 Analysis for the content of Br, P, Cl, Sn, b, F by EDXRF
  • 2.2.11 Migration test in artificial sweat and artificial saliva, respectively
  • 2.2.12 Analysis of volatile organic components (VOC) by headspace analysis
  • 2.2.13 Analysis of isocyantes with HPLC
• 2.3 Analysis results divided according to sample types
  • 2.3.1 Foam wash cloths
  • 2.3.2 Pillows for feeding the baby
  • 2.3.3 Baby mattresses
  • 2.3.4 Nursing pillows
  • 2.3.5 Baby carriers
  • 2.3.6 Apron for perambulators
• 2.4 Analysis results for specific analyses according to analysis type
  • 2.4.1 Analysis results for arylamines
  • 2.4.2 Analysis results for disperse colourants
  • 2.4.3 Analysis results for P-containing flame retardants [µg/g]
  • 2.4.4 EDXRF analysis - results presented as % (w/w)
  • 2.4.5 Analysis results for organic tin compounds
  • 2.4.6 Chlorinated benzenes and toluenes
  • 2.4.7 Analysis results for chlorinated phenols and OPP
  • 2.4.8 Analysis results for phthalates, mg/g
  • 2.4.9 Formaldehyde
  • 2.4.10 Migration test in sweat of selected products
  • 2.4.11 Migration test in saliva for selected products
  • 2.4.12 Migration test in sweat and saliva for PS-pellets
  • 2.4.13 Emission test of volatile organic components - PS-pellets
• 2.5 Selection of chemical substances for evaluation

To ensure optimal clearness, the chapter concerning the chemical analyses has been subdivided according to types of products.

• Foam wash cloths (disposable wash cloths)
• Pillows for feeding the baby
• Mattresses
• Nursing pillows
• Baby carriers
• Apron for perambulators.

2.1 Analysis programme

Some of the examined products are composed of several elements and where considered relevant these elements are examined individually as the different materials calls for different analysis method.

2.1.1 Foam materials

Under this material designation belongs the following products or parts of products:

• Foam wash cloths
• Foam mattresses
• Foam in nursing pillows
• Foam in baby carriers.

For the detection of possible content of flame retardants, organic tin compounds, tin and antimony for all foam materials are performed a screening analysis by EDXRF to measure chromium, chlorine, phosphorous, tin and antimony.

Products where tin is determined are supplemented with a specific analysis for the content of organic tin compounds.

For all foam materials, a screening analysis by GC-MS for the contents of volatile organic components is preformed. By this determination, a further specific analysis for the content of phosphorous flame retardants is performed.

A specific analysis for certain isocyanates (MDI and TDI) has been performed on the three types of foam wash cloths using the HPLC method.

2.1.2 Textiles

Under this material designation belongs the following part of products:

• Cover on foam mattresses
• Cover on pillows for feeding the baby
• Cover on nursing pillows
• Textiles on baby carriers.

Textiles of cotton are examined for their content of formaldehyde. Coloured textiles are examined contents of azo-colourants and disperse colourants.

Synthetic fabrics are examined for contents of chlorinated phenols – tetrachlorophenol (TeCP) and pentachlorophenol (PCP), - 2-phenylphenol (OPP), for the content of chlorinated benzenes and chlorinated toluenes.

For selected textiles a screening analysis by GC-MS for the content of volatile organic components (VOC) has been performed.

For the detection of possible content of flame retardants, surface treated textiles are analysed by an EDXRF-screening to measure bromine, chlorine and phosphorous. In this context a further measurements for the contents of fluorine and sulphur was performed to the identification of potential content of PFOS compounds.

2.1.3 Polymer materials

Under this material designation is included the following part of products:

• Cover of nursing pillows
• Labels, buckles, etc.

All polymer materials including textiles surface treated with polymer materials are examined for contents of phthalate based plasticizers.

For selected products, a screening analysis by GC-MS for contents of volatile organic compounds has been performed.

2.1.4 Polystyrene pellets

Under this material designation is included the following part of products:

• Stuffing material in pillows for feeding the baby.

To determine possible content of flame retardants the polystyrene pellets have been examined by an EDXRF screening analysis to measure for bromine, chlorine and phosphorous.

A screening analysis by GC-MS for the content of volatile organic compounds has been performed.

2.1.5 Summary of performed analyses

Table 2.1 and Table 2.3 summarise which analyses that have been performed on the different materials and subsamples

Table 2.1 Summary of analysis parameters related to materials

Summary of selected baby products and the analysed subsamples is presented in Table 2.2.

Table 2.2 Summary of selected baby products and the analysed subsamples

The analysis programme for the selected baby products was established based on the composition of the materials, knowledge to the material character and experience from published and corresponding studies. Summary of the analysis programme is presented in Table 2.3.

Table 2.3 Summary of analysis programme for baby products distributed in subsamples

2.2 Methods

A representative amount of sample or a represenative area of the tested materials were removed for analysis. The analyses were performed by double determination according to the following methods.

2.2.1 Analysis for content of azo-colourants

The analysis was performed according to DS/EN 14362-1. A weighed amount of sample, approx. 1 g, was extracted in a buffer solution at 70ºC for 30 minutes after the addition of internal standards of aniline-d₄ and naphthaline-d₈. Then a solution of sodium dithionite was added and the sample was left for 30 minutes at 70ºC. The concentration was increased on SPE-filter followed by extraction using MTBE. The extract was analysed by gaschromatography-mass spectrometry (GC-MS in scan mode).

Quantification performed against external standards of each of the analytes.

A summary of the azo-colourants screened for is presented in Table 2.4.

The detection limit are for all components 5 µg/g.

Table 2.4 Summary of azo-colourants

2.2.2 Analysis for content of disperse colourants

A weighted amount of sample, 1 to 5 g, was extracted in acetone by ASE-extraction or Soxhlet extraction. The extracts were analysed for their content of disperse colourants by TLC using different solvents.

Determinations were performed against external standards of each of the analytes.

Table 2.5 presents the disperse colourants that were screened for.

Table 2.5 List of measured disperse colourants

2.2.3 Analysis of the content of selected organic tin compounds

A weighed amount of sample, 0.5 to 1 g, was extracted in 70 ml acid methanol by ultrasound for 2 hours. After pH adjustment with sodium hydroxide a solution of sodium tetraethylborate was added. After 1 hour reaction at mechanical shaking the extract was transferred to a SPE-filter which was then extracted by isooctane. The extract was analysed by gaschromatography-mass spectrometry (GC-MS in scan mode).

Quantification was performed against external standards of each of the analytes (selected organic tin compounds).

Table 2.6 presents the organic tin compounds that were screened for. The detection limit for the used analysis method was 0.02 µg/g.

Table 2.6 List of organic tin compounds

2.2.4 Analysis of the content of selected organic phosphorous compounds

A weighed amount of sample, 0.5 to 2 g, was extracted in 25 ml dichloromethane for 2 hours by mechanical shaking. The extract was analysed by gaschromatography-mass spectrometry (GC-MS in scan mode).

Quantification was performed against external standards of each of the analytes.

Table 2.7 presents the organic P-compounds screened for. The detection limit of the used analysis method is 1 µg/g.

Table 2.7 List of P-compounds screened for

2.2.5 Analysis of content of chlorinated benzenes and toluenes

A weighed amount of sample, approx. 2 g, was extracted in 40 ml acetone added internal standards of C₁₃-labelled hexachlorobenzene for 2 hours by mechanical shaking. The extracts were concentrated and analysed by gaschromatography-mass spectrometry (GC-MS in scan mode).

Quantification was performed against external standards of each of the analytes.

In connection to the performed determinations, dichloro-, trichloro-, tetrachloro-, pentachloro-, hexachlorobenzenes, and chloro-, dichloro-, trichloro-, tetrachloro-and pentachlorotoluenes were analysed for.

The detection limit for the used analysis method is 0.05 µg/g.

2.2.6 Analysis for content of chlorinated phenols and OPP

A weighed amount of sample, approx. 5 g, was added internal standards of C₁₃-labelled pentachlorophenol and extracted in a solution of K₂CO₃ by ultrasonic extraction. Derivatization by acetic acid anhydride followed by extraction by hexane. The extract was concentrated and analysed by gaschromatography-mass spectrometry (GC-MS in SIM mode).

Quantification was performed against external standards of each of the analytes.

Table 2.8 presents the chlorinated phenols and OPP screened for and the detection limit for the used analytical method.

Table 2.8 Detection limit for chlorinated phenols and OPP

2.2.7 Analysis for content of selected phthalates

A weighed amount of sample, 0.1 to 1 g, was extracted in 20 ml dichloromethane added internal standards of BBP-d₄ and DEHP-d₄ by mechanical shaking for 2 hours. The extract was analysed by gaschromatography-mass spectrometry (GC-MS in scan mode).

Quantification was performed against external standards of each of the analytes.

Table 2.9 presents the phthalates screened for and the detection limits of the used analytical methods.

Table 2.9 Detection limit of determined phthalates

2.2.8 Analysis for content of formaldehyde

The content of formaldehyde was determined according to standard method ISO 14184-1:1998 (spectrometry). The detection limit of the used method is 20 µg/g.

%RSD = 3.

2.2.9 Screening analyse by GC-MS

A weighed amount of sample, 0.5 to 3 g, was extracted in 25 ml dichloromethane added internal standards of ethylbenzene-d₁₀, chlorobenzene-d₅, pyrene-d₁₀ and DEHP-d₄ by mechanical shaking for 2 hours. The extract was analysed by gaschromatography-mass spectrometry (GC-MS in scan mode).

The components were identified by comparison of the relevant mass spectres with mass spectres in the NIST library.

Semi-quantitative determination was performed against the internal standards and selected analytes.

2.2.10 Analysis for the content of Br, P, Cl, Sn, b, F by EDXRF

Analysis by x-ray technique (energy-dispersive X-ray fluorescence (EDXRF)

Philips PW2400/UNIQuant ver. 4.51). The detection limit for the used analytical method is 0.001 %w/w.

2.2.11 Migration test in artificial sweat and artificial saliva, respectively

Selected samples were examined for migration of organic compounds to simulated sweat and saliva.

A representative area of material was removed and extracted in artificial sweat and artificial saliva (saliva solution), respectively, in an end-over-end shaker in an incubator at 37ºC for 4 hours. The extract was decanted to a separatory funnel, added internal standards of toluene-d₈, ethylbenzene-d₁₀, naphthalene-d₈ and DEHP-d₄ and then extracted by dichloromethane. The resulting extracts were analysed by gaschromatography-mass spectrometry (GC-MS in scan mode).

Quantitative determination was performed against internal standards and selected analytes.

The procentual relative standard deviation based on duplicate analyses was estimated to 10-15% for the reported analytes in the analyzed material.

Equipment used for the above mentioned GC-MS analyses.

A HP gaschromatograph 5890 with a HP mass spectrometer 5972 was used.

Analysis parameters

2.2.12 Analysis of volatile organic components (VOC) by headspace analysis

A weighed amount/area of sample was transferred to a 5 L glass container (emission chamber). Air samples were extracted by a membrane air pump and collected on a solid adsorbent (Tenax TA). The Tenax filters were exposed during 3 succeeding time periods of 60 minutes.

The Tenax filters were then analysed by thermic desorption combined with gas chromatography-mass spectrometry (ATD/GC-MS in scan mode).

Components were identified by comparison of the respective mass spectres with the mass spectres from the NIST library.

The amount of detected components was determined against external standards of toluene.

Equipment

A Perkin-Elmer TurboMass Mass spectrometer with Perkin-Elmer ATD 400 was used for the analysis.

Analysis parameters

2.2.13 Analysis of isocyantes with HPLC

A sample of approximately 3 gram was extracted with 130 ml dichloromethane. The concentration of the extract was increased and the content of isocyanates was derivatized by piperazin.

The following quantitative analysis was made by liquid chromatography with HPLC combined with fluorescence detection.

2.3 Analysis results divided according to sample types

The analysis results for the performed determinations are divided into the individual product types. For the specific analyses an empty box means that the analysis in question was not performed for the concerned sample. For the screenings of volatile organic components, an empty box means that the substance in question was not detected in the concerned sample.

2.3.1 Foam wash cloths

The analysis results for the measurements performed on foam wash cloths are summarised in Table 2.10 and Table 2.11.

Table 2.10 Specific analyses – foam wash cloths

*The analysis uncertainty is between 5-10% for these compounds

Table 2.11 Screening for volatile organic compounds – foam wash cloths

”+” Indicates that a content of the component has been found in connection with the used analysis method.
i.p. = Not detected
*The analysis uncertainty is between 10-25% for these compounds

Table 2.12 Specific analysis for selected isocyanates – foam wash cloths

2.3.2 Pillows for feeding the baby

The analysis results for measurements performed on pillows for feeding the baby is summarised in Table 2.13 and Table 2.14.

Table 2.13 Specific analyses – Pillows for feeding the baby

*The analysis uncertainty is between 5-10% for these compounds

Table 2.14 Screening for volatile organic compounds – pillows for feeding baby

i.p. = Not detected
*The analysis uncertainty is between 10-25% for these compounds

2.3.3 Baby mattresses

The analysis results for measurements performed on mattresses is summarised in Table 2.15 and Table 2.16.

Table 2.15 Specific analyses – baby mattresses

i.a. = Not analysed
*The analysis uncertainty is between 5-10% for these compounds

Table 2.16 Screening for volatile organic components – baby mattresses

*The analysis uncertainty is between 10-25% for these compounds
**2582: Sum of 3 isomer peaks of 484+976+1122 µg/g, respectively
*** 715: Sum of 2 isomer peaks of 622+93 µg/g, respectively
”+” Indicates that a content of the component has been found in connection with the used analysis method.
i.p. = Not detected

2.3.4 Nursing pillows

The analysis results of the measurements performed on mattresses are summarised in Table 2.17 and Table 2.18.

Table 2.17 Specific analyses – nursing pillows

*The analysis uncertainty is between 5-10% for these compounds
i.a. = not analysed

Table 2.18 Screening for volatile organic compounds – nursing pillows

*The analysis uncertainty is between 10-25% for these compounds
”+” Indicates that a content of the component has been found in connection with the used analysis method.
i.p. = Not detected

2.3.5 Baby carriers

Table 2.19 Specific analyses – baby carriers

*The analysis uncertainty is between 10-25% for these compounds
**The analysis uncertainty is 5-10 for these compounds
i.a. = Not analysed

2.3.6 Apron for perambulators

Table 2.20 Specific analyses – apron for perambulators

*The analysis uncertainty is between 10-25% for these compounds
**The analysis uncertainty is 5-10 for these compounds
*** Analyses have been performed on both inner and outer side. Both results are stated.
i.p. = Not detected
i.a. = Not analysed

Table 2.21 Screening for volatile organic components – apron to perambulators

*The analysis uncertainty is between 10-25% for these compounds
”+” Indicates that a content of the component has been found in connection with the used analysis method.
i.p. = Not detected

2.4 Analysis results for specific analyses according to analysis type

2.4.1 Analysis results for arylamines

The samples marked 9A, iB, 9C, 10A, 10B, 10C, and 12A: Content of selected arylamines above the detection limit of 5 µm/g was not detected.

2.4.2 Analysis results for disperse colourants

Table 2.22 Results for disperse colourants

*The detection limit for disperse colourants is 50 µg/g and the analysis uncertainty is 10-20%

2.4.3 Analysis results for P-containing flame retardants [µg/g]

Table 2.23 Results for P-containing flame retardants

*The detection limit for r P-containing flame retardants is 1 µg/g and the analysis uncertainty is 5-10%

2.4.4 EDXRF analysis – results presented as % (w/w)

Table 2.24 Results EDXRF analysis

’*’ means that the sample has not been analysed for content of fluor (F).
i.a. = Not analysed
The detection limit is 0.001 % (w/w)

2.4.5 Analysis results for organic tin compounds

Samples marked 1, 2, 3, 5C, 6B, 7B, 8B, 9D, 10H, 11D, 11E, 12A, 12D and 13B: There was not detected any content of selected organic tin compound above the detection limit of 0.02 µg/g.

2.4.6 Chlorinated benzenes and toluenes

Samples marked 9A, 9B, 9C, 11A and 12A: There was not detected any content of chlorinated benzenes and toluenes above the detection limit of 0.05 µg/g.

2.4.7 Analysis results for chlorinated phenols and OPP

Table 2.25 Results for chlorinated phenols and OPP

The analysis uncertainty is 5-10% for all compounds

2.4.8 Analysis results for phthalates, mg/g

Table 2.26 Results for phthalates

Values separated by oblique stroke indicate results of single determinations.
The analysis uncertain is 5-10% for phthalates

2.4.9 Formaldehyde

Table 2.27 results for formaldehyde

The detection limit for formaldehyde is 20 µg/g and the uncertainty is 5-10%

2.4.10 Migration test in sweat of selected products

Samples 4A, 5A, 7A, 8A, 13B, and 13C have been selected for migration test in sweat, as these products are normally in direct skin contact. Further, 4C and 5C (PS-pellets) were selected, see table 2.33.

The results of performed migration tests in sweat for selected samples are summarised in Table 2.28, Table 2.29, Table 2.30, and Table 2.31.

The analysis uncertainty of the migration tests is 5-15%.

Table 2.28 Results of performed migration tests in sweat for selected subsamples

Table 2.29 Results of migration test performed in sweat for selected subsamples

>¹ measured with HPLC

Table 2.30 Results of migration test performed in sweat for selected subsamples

Table 2.31 Results of migration test in saliva for selected subsamples

”+” Indicates that a content of the component has been found in connection with the used analysis method.

2.4.11 Migration test in saliva for selected products

Samples 11A and 12A were selected for migration test in saliva, as babies are often in direct mouth contact with these materials. Further samples 4C and 5C (PS pellets) were selected, see Table 2.33.

The results for the performed migration test in saliva for selected products are summarised in Table 2.32.

The uncertainty of the migration tests is 5-15%.

Table 2.32 Results of migration test in saliva for selected products

2.4.12 Migration test in sweat and saliva for PS-pellets

The results of the migration test in sweat and saliva for polystyrene (PS) pellets are summarised in Table 2.33.

The analysis uncertainty is 5-15%.

Table 2.33 Results of migration test in sweat and saliva for PS-pellets

Sample 4C: 1.0 g of sample corresponds to approx. 80 ml. Total weight of PS-pellets in the baby feeding pillow: 350-400 g.

Sample 5C: 1.0 g sample corresponds to approx. 80 ml. Total weight of PS-pellets in the baby feeding pillow: 350-400 g.

2.4.13 Emission test of volatile organic components – PS-pellets

The results of the performed emission test of VOC for PS-pellets are summarised in Table 2.34.

The analysis uncertainty of the tests is 5-15%.

Table 2.34 Results of performed emission test for volatile organic components in PS-pellets

Sample 4C: 3.0 g sample corresponds to 250 ml. Total weight of PS-pellets: 350-400 g.

Sample 5C: 3.1 g sample corresponds to 250 ml. Total weight of PS-pellets: 350-400 g.

Exposure in 5 l climate chamber:

The air change was once every second hour

2.5 Selection of chemical substances for evaluation

Out of the identified substances and based on classification and occurrence was selected a number of substances for further evaluation of a possible health risk to consumers. The consumer is in this context defined as children at the age of 0 to 1 year.

In co-operation with the Danish Environmental Protection Agency 10 substances for health and environmental assessment are selected. The substances are presented in Table 2.35.

Table 2.35 Summary of selected substances

”+” Indicates that a content of the component has been found in connection with the used analysis method.

| Front page | | Contents | | Previous | | Next | | Top |

Version 1.0 March 2008, © Danish Environmental Protection Agency