Kortlægning af kemiske stoffer i forbrugerprodukter, Nr. 84 2007 – Kortlægning samt sundhedsmæssig vurdering af kemiske stoffer i skoletasker, legetasker, penalhuse og viskelædere

Kortlægning samt sundhedsmæssig vurdering af kemiske stoffer i skoletasker, legetasker, penalhuse og viskelædere

Summary and conclusions

As a 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 rubber erasers is wanted. The project Survey as well as environmental and health assessment of chemical substances in school bags, toy bags, pencil cases and rubber erasers is conducted in three phases. The survey includes mapping of the market, qualitative and quantitative analyses as well as health assessment of possible harmful impacts from substances being emitted from school bags, toy bags, pencil cases and rubber 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 direct is made. This information is provided in four ways:

Search via the Internet
Purchase of school bags, toy bags, pencil cases and rubber 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 rubber erasers are bought. These 26 pieces of rubber erasers represent a wide choice of the types of rubber erasers which are found on the market today. Also based on the market analysis the most used 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 rubber 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. An indication of the presence of MBT at the FT-IR screening is also obtained.
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 as 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 as screening on all polymers. In the project screening for chlorine on a number of products including a large number of rubber erasers is conducted.
Quantitative determination of phthalates in a large number of rubber erasers and migration to 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 underlining of products containing chromium, arsenic, selenium, antimony, cadmium, barium, mercury and lead as these substances must not be higher than 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 determined that some of the products emit a chemical odour, especially when they are quite new. Therefore, it is analyzed which volatile compounds being emitted to the air when handling the products. The analysis is conducted semi-quantitatively by means of headspace technique combined with GC-MS.
Screening for spillover 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 test, the FT-IR analysis and the XRF analysis showed that the 9 out of 26 of the rubber 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. Titan is measured in some of the products and is probably integrated as a white pigment in the form of titandioxide.

Furthermore, that XRF analysis has shown a high content of Cr, As, Se, Cd, Sb, Ba, Hg and/or Pb in one or more products. Based on the chosen analysis programme these products are not analyzed further via migration analyses and therefore these are not selected for a more detailed health assessment.

In total, four products exceed the application limitations for lead and cadmium as described in chapter 2, Legislation (no overrun 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 found. Of these, 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 found. 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 large.

Phase 3

A risk assessment is made for the content of the following 11 substances being identified via headspace (i.e. evaporate 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 rubber erasers there is a potential of exposure via the mouth, for instance when the children chew and suck the rubber erasers. At oral exposure the absorption takes place after emission (migration) of the substances from the rubber erasers and mixture in saliva. Absorption is presumed to take place via the mucous membranes in the mouth cavity or in the gastrointestinal tract.

Migration analyses for artificial saliva are made 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 via use of pencil case, rubber eraser and school bag and at exposure via both inhalation and migration for artificial sweat.

Some of the studied rubber erasers are made of PVC (9 of 26) and four of these rubber erasers have a content of DEHP as plasticizer. Daily intake of a small amount (cube of approx. 4 mm) of rubber 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 or chews on a rubber 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 rubber 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.

Forkortelser

ADI	Acceptabelt dagligt indtag. Estimeret indtag som antages ikke at have skadelig effekt. Kan være akut eller kronisk. Er som regel baseret på indholdsstoffer i fødevarer (additiver)
DL	Detektionsgrænse (detection limit)
EC	Effekt koncentration (effect concentration)
EC₅₀	Median effekt koncentration, dvs. den koncentration hvor 50% af forsøgsdyrene viser en effekt
LC₅₀	Median letal koncentration, dvs. den koncentration hvor 50% af forsøgsdyrene er døde
LD₅₀	Median letal dosis, dvs. den dosis hvor 50% af forsøgsdyrene er døde
lgv	Legemsvægt
LOAEL	Den laveste fundne koncentration med skadelige effekter (Lowest Observed Adverse Effect Level)
MAK	Maksimaler Arbeitsplatz Konzentration: Grænseværdi for arbejdsmiljø defineret af tyske arbejdsmiljømyndigheder
MOS	Margin of Safety. Sikkerhedsmargin, som er forholdet mellem den estimerede eksponering og den koncentration, der anses for ikke at ville medføre nogen sundhedsrisiko (f.eks. NOAEL)
NOAEL	Den største koncentration, hvor der ikke er observeret skadelige effekter (No-Adverse-Effect Level)
RfC	Inhalation Reference Concentration. En koncentration (f.eks. µg/m³), som er et estimat af en daglig eksponering ved inhalation, som antages uden væsentlig skadelig effekt ved inhalation over et menneskes levetid. Det antages, at der findes en grænseværdi for den toksiske effekt, som værdien er afledt af
RfD	Oral Reference Dosis, som er et estimat af en daglig indtagelse ( f.eks. µg/kg lgv/dag), som antages uden væsentlig skadelig effekt ved indtagelse over et menneskes levetid. Det antages, at der findes en grænseværdi for den toksiske effekt, som værdien er afledt af
t	Timer
TDI	Tolerabelt dagligt indtag. Estimeret indtag som antages ikke at have skadelig effekt. Kan være akut eller kronisk. Er som regel baseret på forurenende kemiske stoffer.
TGD	Technical Guidance Document: EU vejledning i risikovurdering af kemiske stoffer
TLV	Grænseværdi (Threshold Limit Value), der er baseret på 8 timers tidsvægtet gennemsnitlig eksponering i arbejdsmiljøet (en arbejdsdag)
TWA	Tidsvægtet gennemsnit (Time Weighted Average)