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Release of chemical substances from tents and tunnels for children

4 Screening of health effects

• 4.1 Method for screening
• 4.2 Screening of substances
  • 4.2.1 Supplementary data
• 4.3 Potentially problematic substances in the screening
  • 4.3.1 Selection of potentially problematic substances
  • 4.3.2 The existence of potentially problematic substances
• 4.4 Non problematic substances in the screening of effects on the health

In the present chapter a screening is presented for the health effects of the substances, which have been detected in the test programme.

The results of the analysis clearly show that the maximum concentration of the emitted substances from the test material has been measured after three hours. Regarding the time-depending emissions, the concentrations are lower both before and after the three hours. Therefore, the screening is based on the three-hour results.

Not all the substances have been found in the same tests. Table 4.1 shows an outline of the substances and the concentrations that have been found in all the six tests measured three hours after the tents and tunnels have been unpacked.

4.1 Method for screening

The object of the screening is to point out the substances that may cause a potential health risk for children when playing with the products.

Each substance is found in more than one product. In the screening, the highest measured concentration of each substance has been used for a conservative evaluation.

It has been checked whether the substances are included in the list on dangerous substances (the Danish statutory order no 439, 2002) or the guideline of self-classification of dangerous substances of the Danish EPA.

As for the substances for which threshold limit values (TLV) in the working environment have been determined, the values have also been used (At-vejledning C.0.1, 2002).

The substances for which the highest concentration constitutes less than 1 % of the TLV and for which no long-term effects have been detected sorted out at first.

For a number of the substances no classification or no TLV has been determined. In table 4.1 these substances are registered with "*". It indicates that there is no TLV for substance or the substance is not classified or both the priors mentioned. The screening of these substances is discussed in section 4.2.

Table 4.1 Outline on the measured substances and their concentrations after three hours in the climatic chamber

4.2 Screening of substances

All the substances in table 4.1 have been screened. In table 4.1 the classification of the substances appearing on the list on dangerous substances is listed. Furthermore, it has been monitored whether a TLV has been determined.

If neither a TLV nor a classification of a substance have been determined a screening has been carried out in anticipation of finding supplementary data on substances that, in structure, are similar to the substance in question. The substances, for which supplementary data have been retrieved, are marked with an "*" in table 4.1.

4.2.1 Supplementary data

4.2.1.1 1,2-Propandiol

The substance 1,2-propandiol with CAS-no 4254-15-3 is not classified and no TLV has been established. CAS-no 4254-15-3 represents (S)-(+)-1,2-Propanediol. The CAS-no 57-55-6, representing 1,2-Propanediol or propylene glycol, has been used in the additional search.

Propylene glycol has no limit value; but an average eight hour mean limit of eight hours at 50 ppm has been retrieved (AIHA 1999) (Workplace Environmental Exposure Level). The limit corresponds to 155 mg/m³. Ethylene glycol has a limit value of 26 mg/m³. In the present screening it is assumed that propylene glycol has a TLV at a level corresponding to 50 mg/m³.

4.2.1.2 1-Butoxy-2-propanol

The substance 1-butoxy-2-propanol with CAS-no 5131-66-8 is classified to be irritating to eyes and skin (Xi;R36/38).

No TLV has been established for the substance. Its structure resembles the substance butoxyethanol (CAS-no 111-76-2), that has a TLV of 98 mg/m³ and with the comment ”may penetrate the skin”.

In the present screening it is therefore assumed that 1-butoxy-2-propanol has a TLV at a level corresponding to 100 mg/m³.

4.2.1.3 2-Ethyl-1-hexanol

The substance 2-ethyl-1-hexanol has CAS-no 104-76-7. Official classification of the substance does not exist nor has the substance a TLV.

The substance is a C8-alcohol. To a certain extent the alcohol 1-octanol with CAS-no 111-87-5 is similar to the substance. As for 1-octanol AIHA stated in 1999 an average eight hours mean value to be 50 ppm per workday (8 hours)(Workplace Environmental Exposure Level). Such a limit corresponds to 266 mg/m³.

The substance 1-hexanol (CAS-no 111-27-3) is classified Xn; R22. In Gosselin et al., 1976, it is stated that 2-ethylhexanol is similar to butyl alcohol regarding toxicity. As a conservative preliminary assessment of the substance the following classification is therefore used for butanol (R10 Xn;R22 Xi;R37/38-41 R67).

4.2.1.4 3-Caren and α-pinene

The substance 3-caren (CAS-no 13466-78-9) is a double-cyclic compound with seven carbon atoms and three methyl groups. α-pinene is also a double-cyclic compound with seven carbon atoms and three methyl groups. The substances are described as terpenes.

Both compounds are very rarely described in the literature. aα-pinene is classified according to the guideline of the Danish EPA as hazardous to the environment with N; R51/53, toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment.

Carene and pinene resembles in their structure to a certain extent to turpentine. Turpentine has CAS-no 8006-64-2 and is classified as hazardous to the health and hazardous to the environment (R10 Xn; R20/R21/22-65 Xi; R36/38 R43 N;R51/53). Turpentine has a limit value of 140 mg/m³.

The terpene limonene (CAS-no 138-86-3) is also classified as R10 Xi; R38 R43 N; R50/53.

It is therefore assumed that carene and pinene are hazardous to the health, may cause allergic reactions and are hazardous to the environment. Data on turpentine are used in the following assessment.

4.2.1.5 4-Methyl-1-pentanol

The substance 4-methyl-1-pentanol has CAS-no 626-89-1. The substance is not classified and it is assumed in the present connection to have properties similar to those of 4-methyl-2-pentanol (108-11-2). This substance is classified R10 Xi; R37, and the classification is used in the present screening.

Pentanol has as a TLV of 360 mg/m³. As methyl pentanol is not likely to have a lower limit value than pentanol, the limit value of pentanol is therefore used in the present screening.

4.2.1.6 Benzaldehyde

Benzaldehyde (100-52-7) is classified as Dangerous to the Health, Xn; R22.

The substance has no Danish TLV, but AIHA 1999 indicates an average eight hours mean value of 2 ppm (Workplace Environmental Exposure Level). Such a limit corresponds to 8 mg/m³. This TLV is used in the present screening.

4.2.1.7 2,6-Di-tert-butyl-p-cresol

The substance 2,6-di-tert-butyl-p-cresol also called BHT has CAS-no 128-37-0. As the substance is not classified the substance is assessed as cresol in the present screening.

Cresol is toxic and corrosive and is classified T; C, R24/25-34. The limit value for cresol is 22 mg/m³.

4.2.1.8 Aliphatic carbon hydrides

In the analyses a number of not further identified aliphatic carbon hydrides have been detected with chain lengths of C₁₀ to C₁₆. They can be linear or branched and have one or more double bonds. The analysis showed that the carbons hydrides do not consist of aromatic compounds.

On the list on dangerous substances the group alkanes, C_12-26, is mentioned. The group is given the CAS-no 90622-53-0 and index-no 649-242-00-4. Group is classified Carc2; R45.

It is also stated that the category described as hydrocarbons, C9-16, hydrogen treated and de-aromatised. The CAS-no 93763-35-0 is stated and an index-no 649-429-00-0. The classification is Xn; R65.

As the analyses show the hydrocarbon fraction does not contain aromates but whether or not the substances may be carcinogenic, cannot be determined. At present it is therefore assessed that substances may be carcinogenic. As it has not been possible to distinguish between the different substances, the fraction in question, C10-C16, is assessed as one compound.

The substance tetramethyl octane may be 2,2,7,7-tetramethyloctan. The molecular formula is C₁₂H₂₆ and can therefore be described as being part of the group of aliphates C_12-16. The compound of tetramethyl octane is therefore assessed along with the other aliphatic carbon hydrides.

Solvent naphtha is a hydrocarbon with a boiling interval 150-205°C. It resembles aliphatic hydrocarbons with a carbon chain of about C_10-16. Solvent naphtha has CAS-no 8052-41-3, index-no 649-345-00-4 and the classification is R10 Carc2; R45 Xn; R48/20-65. Solvent naphtha has a TLV of 145 mg/m³. In the present report these data are used as the basis for the assessment.

4.2.1.9 Aldehyde

In the analyses a number of aldehydes have been detected. They are shown in table 4.2.

Table 4.2 Aldehydes and their properties

Aldehydes are generally irritating to skin and eyes and may be irritating to the respiratory system. A part of the aldehydes can be used as additives for food.

As for propanal, no risk occur to the central nervous system and the blood after inhalation of concentration less than 0.5 mg/m³ (Tokanova, 1982).

The substance butanal is classified as very combustible with F; R11. The substance has no Danish TLV, but AIHA 2001 indicates an average eight hours mean limit of 25 ppm (Workplace Environmental Exposure Level) Such a limit corresponds to 74 mg/m³.

Pentanal is also described as valeraldehyde and has a TLV of 175 mg/m³.

Saturated aldehydes as pentanal and hexanal are not toxic (Kaneko, 1988).

No TLVs for hexanal, heptanal, octanal, nonal and decanal have been detected.

Nonal and decanal is included in the guideline for dangerous substance of the Danish EPA and is classified as Dangerous to the Environment. Nonal is classified N; R50, and decanal is classified N; R50/53.

For the preliminary screening a TLV of 0.5 mg/m³ for propanal, 74 mg/m³ for butanal, and 175 mg/m³ for other aldehydes is used.

4.3 Potentially problematic substances in the screening

4.3.1 Selection of potentially problematic substances

The substances, detected in the analyses, which are described as potentially problematic substances, are shown in table 4.3.

The data, emphasised by a grey colour in table 4.3, are estimated data. The arguments for the estimations are described in subsection 4.2.1.

Table 4.3 includes the substances, known for having or under suspicion of causing long-term effect and/or where the measured concentration constitutes more than 1 % of the TLV.

An estimated TLV for aliphatic hydrocarbons C₁₀-C₁₆ is shown in table 4.3. The hydrocarbons are solely assessed based on the fact that they may be carcinogenic. At the same time they appear in the analyses in a relatively high concentration.

Table 4.3 List on potentially problematic substances

As shown in table 4.3 the detected concentrations for dimethyl formamide, formaldehyde and hydrocarbons C10-C16 and phenol are relatively high.

Compared with the TLVs the measured concentrations represent more than 1% of the TLV of

• formaldehyde
• dimethyl formamide

Among the selected substances the group of hydrocarbons, aliphates with carbon chains at C10-16 are classified as carcinogenic in category 2 (Carc2).

Ethoxyethanole is teratogenic (Rep2; R60-61). Dimethyl formamide is also teratogenic (Rep2; R61).

Among the selected substances the following substance are under the suspicion of causing cancer (Carc3; R40):

• Acetaldehyde
• Formaldehyde
• Tetrachloroethylen
• Trimethylhexen-1-on

The substances α-pinene and 3-caren may cause sensitisation by skin contact. (Xn; R43).

Phenol is toxic and corrosive. The substance 2,6-di-tert-butyl-p-crecol has probably the same properties and therefore both substances are mentioned.

In addition the following substances are selected as being significant as agreed with the Danish EPA:

• 2-Butoxyethanol
• xylene
• toluene

4.3.2 The existence of potentially problematic substances

The preliminary screening is based on the highest measured values. Table 4.4 shows in which products the substances are found and in which concentrations.

In analyses of 3-caren and α-pinene blind values (background values) between 1 and 3 µg/m³ have been measured. It indicates that the measured values of these substances of less than 5 µg/m³ may be considered uncertainty/pollutants

As for the hydrocarbons C10-C16 blind values between 10 and 20 µg/m³ have been measured implying that the blind values do no significant influence in the interpretation of the results.

The blind values of formaldehyde, dimethyl formamide and 2-butoxyethanol are below 1 µµg/m³.

The results of analyses shown in table 4.4 are adjusted according to the blind values.

Table 4.4 Overview of results of the analyses on selected substances.

In sample A, the substances detected are primarily dimethyl formamide, 2,6-di-tert-butyl-p-cresol, formaldehyde and aliphatic hydrocarbons. In addition acetaldehyde has been detected, which is under the suspicion of causing cancer, and 3-caren and α-pinene, which cause sensitisation by skin contact.

In sample B a high concentration of formaldehyde and aliphatic hydrocarbons have been detected. In addition 3-caren and α-pinene have been detected as well, which may cause sensitisation by skin contact.

In sample C high concentrations of formaldehyde and aliphatic hydrocarbons have been detected. In addition acetaldehyde has been detected, which is under suspicion of causing cancer.

Sample D is characterised by high concentrations of 2-Butoxyethanol, formaldehyde and aliphatic hydrocarbons. Dimethyl formamide, which is present in relatively small quantities, is teratogenic. Likewise small quantities of acetaldehyde and tetrachloroethylen, which are under the suspicion of causing cancer, have been detected.

Sample E is characterised by a certain concentration of aliphatic hydrocarbons, which are carcinogenic, and of dimethyl formamide, which is teratogenic. Likewise formaldehyde and trimethylcyclohexen-1-on, which are under suspicion of causing cancer, have been detected.

Sample F is primarily characterised by high concentrations of aliphatic hydrocarbons, which are carcinogenic. 2-Ethoxyethanol, which is present in a certain quantity, and dimethyl formamide, which is present in a rather low concentration, are both teratogenic. Formaldehyde, which is under the suspicion of causing cancer, appears in a relatively low concentration. In addition α-pinene, which may cause sensitization by skin contact, is present.

4.4 Non problematic substances in the screening of effects on the health

The substances that have been detected as insignificant in the screening among all the identified substances are shown in table 4.5. The values based on assessments are emphasised with a grey background in table 4.5. The assessment is mentioned in subsection 4.2.1.

Table 4.5 Overview on less significant substances detected in the screening

As shown in table 4.5, none of the listed substances are known or under suspicion of having any long-term effects on the health. In addition, the highest measured concentrations pose less than 1% of the limit value.

The substances shown in table 4.5 will not be assessed any further.

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Version 1.0 August 2005, © Danish Environmental Protection Agency