Scented toy story

Those Easter bunnies that look so cute in the stores around this time of year are very tempting. Just the gift for your favourite niece or granddaughter, or even your partner if you are feeling romantic. They might even be scented bunnies, adding to their allure, but that is not always a good thing.

Of the many fragrances used in children's toys, some are allergenic to humans. A study carried out in Denmark in 2006 revealed that 70% of children's products tested contained detectable levels of fragrance allergens, which are one of the most common causes of contact dermatitis in children.

The potential health risks associated with toys prompted the EU to revise its toy safety directive in 2009 for all toys placed onto the EU market, banning 55 fragrances. They can be present up to a low level, 100 µg/g, if it is technically unavoidable. A further 11 fragrances with weaker allergenic potential are allowed at concentrations above this value, as long as they are declared on the packaging.

A team of scientists based in Germany noted that direct contact is not the only way in which people can be contaminated by allergens. By definition, a fragrance is volatile, so it could also be inhaled and still initiate allergenic symptoms. So, this team, comprising Ines Masuck, Christoph Hutzler and Andreas Luch from the Department of Product Safety at the Federal Institute for Risk Assessment in Berlin, undertook a study of the emission of fragrances from toys, as well as their content.

The researchers developed an SPME-GC/MS procedure to measure the emission levels of allergens from scented toys held at 23 and 40°C. In addition, a solid-liquid extraction GC/MS method was applied to measure the allergen contents in the toys themselves. The procedures were used to measure 24 of the 66 allergens listed in the EU Directive, 13 that are banned and 11 that require declaration if present.

Initially, the SPME-GC/MS method was optimised using a mixture of fragrances. Five SPME fibres were found to perform well but an 85 µm polyacrylate fibre was selected because it gave the best combination of recovery, relative standard deviation and subsequent desorption in the GC injection port.

A piece of PVC material impregnated with all 24 allergens was used to determine the best extraction conditions. The optimum extraction time at 23 °C was 4 hours and the equilibration and extraction times at 40°C were set to 4 and 3 hours, respectively.

The fibres were inserted into the GC for analysis, using a cold injection system initialised at 100°C and raised at 12°C/min to 300°C. The fragrance components were allowed 60 s at the maximum temperature to desorb onto a 50% phenyl-methylpolysiloxane column which was also temperature programmed.

The eluting compounds were analysed by electron ionisation and were quantified using one ion each, with a combination of retention time and qualifier ions to confirm their identification. An external calibration curve was used for quantification. The method yielded detection limits which were less than 1 ng/cm3 at 23°C and up to 1.27 ng/cm3 at 40°C.

Allergen contents in the toys themselves, as opposed to the emitted quantities, were measured on the same GC/MS system following extraction of frozen, powdered samples with toluene-ethyl acetate.

The procedures were used to analyse 5 scented dolls purchased from online stores. Some of the dolls contained high levels of the plasticisers diethyl phthalate and diisobutyl adipate, as well as measurable amounts of permitted fragrances.

However, 3 banned fragrances were detected. The contents of coumarin (sweet, vanilla odour) and eugenol (spice, clove-like) were both less than 100 µg/g, which is allowable under the EU legislation. The main offender was benzyl benzoate, which is described as having a sweet, balsamic odour with fruity or berry overtones. It exceeded 100 µg/g in 3 of the dolls, so required declaration on the packaging. This declaration was absent.

Not surprisingly, emissions of the fragrances from the dolls were greater at the higher temperature, although the actual amounts given off depended on the original content in the dolls, as measured by GC/MS.

The results suggest that scented toys might present a risk to children by inhalation, as well as direct contact. Higher emissions at increased temperatures could become important when the child is holding the toy close to its body, or is playing in front of a fire or radiator.

The research team recommended that further studies are required to better characterise and assess the risks for children due to the inhalation of toy fragrance allergens during play.

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Journal of Chromatography A 2010 (Article in Press): "Investigations on the emission of fragrance allergens from scented toys by means of headspace solid-phase microextraction gas chromatography-mass spectrometry"