Survey of Chemical Substances in Consumer Products, No. 84 2007 – Survey as well as health assessment of chemical substances in school bags, toy bags, pencil cases and erasers

Survey as well as health assessment of chemical substances in school bags, toy bags, pencil cases and erasers

Summary and conclusions

As part of the Danish Environmental Protection Agency’s survey of chemical substances in a number of consumer products, knowledge of which substances being a part of and being emitted from school bags, toy bags, pencil cases and erasers is wanted. The project Survey as well as health assessment of chemical substances in school bags, toy bags, pencil cases and erasers is conducted in three phases. The survey includes mapping of the market, qualitative and quantitative analyses as well as a health assessment of possible harmful impacts from substances being emitted from school bags, toy bags, pencil cases and erasers.

Phase 1 includes a study of the types of products which are on the Danish market. Furthermore, a study of which materials they are made of or which materials being a part of them as well as at which age group they are directed at. This information is provided in four ways:

Search via the Internet
Purchase of school bags, toy bags, pencil cases and erasers
Through contact to suppliers and producers whose identity is found on the packaging
Through contact to a number of relevant associations and organizations

Based on the market analysis 26 different pieces of erasers are bought. These 26 pieces of erasers represent a wide choice of the types of erasers which are on the market today. Also based on the market analysis the most frequently bought school bags and a random choice of toy bags and pencil cases are selected.

Phase 2 includes qualitative and quantitative analyses of constituents in school bags, toy bags, pencil cases and erasers. The following analyses of in total 43 products are carried out:

Screening by use of FT-IR for identification of polymeric types, phthalates and to some extent inorganic colouring agents. This analysis is conducted on a part of the products to get an indication of which substances they contain.
Beilstein’s test as verification of the FT-IR analysis with the object of determining whether a polymer is vinyl (PVC). Beilstein’s test is a quick qualitative method for determination of halogens. A little piece of the sample is burnt on a copper wire in a flame. Green colouring of the flame indicates content of chlorine. Beilstein’s test is carried out on all polymers as screening. In the project screening for chlorine on a number of products including a large number of erasers is carried out.
Quantitative determination of phthalates in a large number of erasers and migration to artificial saliva and sweat.
Quantitative determination of elements by use of X-ray analysis (XRF). From the analysis it is indicated whether the sample contains chlorinated or brominated flame retardants, chlorinated anti-bacterial means, tin compounds, sulphur or nickel. Emphasis has especially been on single out products containing chromium, arsenic, selenium, antimony, cadmium, barium, mercury and lead as amount of these substances must not exceed a stated maximum amount at extraction according to the Toys Statutory Order.
ICP-MS analysis of extractions to determine the content of selected metals (chromium, arsenic, selenium, antimony, cadmium, barium, mercury and lead) in the extractions.
GC-MS headspace analysis. It is discovered that some of the products emit a chemical odour, especially when they are quite new. Therefore, an analysis of volatile compounds being emitted to the air when handling the products is carried out. The analysis is conducted by means of semi-quantitative headspace technique combined with GC-MS.
Screening for staining colouring agents through UV-VIS analysis. The result of this analysis has been significant information whether more detailed analyses were needed.
GC-MS for analysis and identification of anti-oxidants and organic colouring agents for assessment of emission of substances from the products to artificial saliva.
Analysis of perfluorinated compounds.

The result of the Beilstein tests, the FT-IR analyses and the XRF analyses showed that 9 out of 26 erasers are made of PVC with phthalate as plasticizer and that both school bags and toy bags are primarily made of polyester textile with plastic parts of PVC with phthalate.

Compared to the results of the FT-IR analysis where a high content of chalk is identified, a high content of calcium in the XRF analysis is correspondingly measured and in many cases also a high content of magnesium. The occurrence of calcium and/or magnesium in the products originates presumably from the use of chalk or dolomite as fillers. Titanium is measured in some of the products and is probably a white pigment in the form of titanium dioxide. The result of the metal analyses in the extractions showed that these metals have not appreciably migrated to the extractions.

Furthermore, the XRF analysis has shown a high content of Cr, As, Se, Cd, Sb, Ba, Hg and/or Pb in one or more products.

In total, four products exceed the application limitations for lead and cadmium as described in chapter 2, Legislation (no violation for mercury).

In a later GC-MS analysis on extracts after extraction in artificial sweat 25 different compounds of interest for a later health assessment are identified. Especially Isophorone, BHT, Cyclohexanone, Phenol, DIBP, DEHP and 2-Heptanone are emphasized as being of particular interest.

In the headspace analysis for volatile substances 23 different compounds of interests for a later health assessment are identified. Of these, especially Isophorone, BHT, Cyclohexanone, Toluene, tert-Butyl alcohol, Methyl propionate and p-Xylene are emphasized as being of particular interest.

The selection is based on the classification of the substances and description of impacts which may be potentially problematic for the consumer if the emission (the migration) of the substances is too high.

Phase 3

A risk assessment is carried out for the content of the following 11 substances being identified via headspace (i.e. evaporation from the products) and/or via migration to artificial sweat or saliva:

Isophorone
BHT
Cyclohexanone
Phenol
Toluene
DIBP
DEHP
2-Heptanone
tert-Butyl alcohol
Methyl propionate
p-Xylene

Regarding the erasers there is a potential of exposure via the mouth, for instance when the children chew or suck the erasers. At oral exposure the absorption takes place after emission (migration) of the substances from the erasers and mixture in saliva. Absorption is presumed to take place via the mucous membranes in the mouth cavity or in the gastrointestinal tract. As children can suck on the erasers these are presumed to be the most interesting product group among school equipment.

Migration analyses for artificial saliva is carried out only for product no. 22 but the results of the migration analyses for artificial sweat are used as a reasonable approximation for the rest of the products.

In general, the content of the above-mentioned substances in the tested products does not present any health risk at normal use of the products; neither in the individual products nor if children are exposed to several products at once – for instance through use of pencil case, eraser and school bag - at exposure via both inhalation and migration for artificial sweat.

Some of the studied erasers are made of PVC (9 of 26) and four of these erasers have a content of DEHP as plasticizer. Daily intake of a small amount (cube of approx. 4 mm) of eraser with a content of DEHP during a longer period may represent a health risk. Correspondingly, it may represent a health risk if a child daily sucks on an eraser with a high content of DEHP during a longer period.

The calculations are generally based on the analyzed values for a few selected school bags, toy bags, pencil cases and erasers. It cannot be rejected that there may be products with a higher content than found in the tested products in this project. Furthermore, there may be other sources to the same chemical substances in the child’s surroundings which will contribute to the total exposure.