7 Analysis for nitrosamines and nitrosatable substances

Analysis of chemical substances in balloons

Balloon nos. 3, 6, 16, and 20 were selected for analysis for nitrosamines and nitrosatable substances according to DS/ EN 12 868, which as previously mentioned is used by analysis of soothers and bottle teats. The selection is made on basis of the TLC screenings and the extraction yields from dichlormethane.

The standard lists 11 nitrosamines, which are causing health concerns in the mentioned products. Below is a list of the nitrosamines found in the analysed balloons with specification of concentrations. TIC is an abbreviation of total ion current by the mass spectroscopic detection.

Table 7.1 Migration of selected nitrosamines - Balloon no. 3

	CAS-no.	Content mg/kg (%RSD)	Detection limit mg/kg
N-nitroso-dimethylamine	62-75-9	0.03* (10)	0.004
N-nitroso-ethylmethylamine	10595-95-6	-	0.005
N-nitroso-diethylamine	55-18-5	-	0.004
N-nitroso-dipropylamine	621-64-7	-	0.005
N-nitroso-dibutylamine	89-16-3	0.08 (14)	0.004
N-nitroso-pyrrolidine	930-55-2	-	0.007
N-nitroso-morpholine	59-89-2	-	0.007
N-nitroso-piperidine	100-95-4	0.003**	0.002
N-nitroso-diphenylamine	86-30-6	-	0.004
Total		0.08-0.11

* Maximum migration. Complete characterisation impossible due to coinciding peaks in TIC of extract..

** Maximum migration. Detected in only one of the two double determinations.

Table7.2 Migration of selected nitrosatable compounds - balloon no. 3

	CAS-no.	Content mg/kg (%RSD)	Detection limit mg/kg
N-nitroso-dimethylamine	62-75-9	2.8 (2)	0.004
N-nitroso-ethylmethylamine	10595-95-6	-	0.005
N-nitroso-diethylamine	55-18-5	-	0.004
N-nitroso-dipropylamine	621-64-7	-	0.005
N-nitroso-dibutylamine	924-16-3	8.1 (25)	0.004
N-nitroso-pyrrolidine	930-55-2	-	0.007
N-nitroso-morpholine	59-89-2	-	0.007
N-nitroso-piperidine	100-95-4	0.01* (2)	0.002
N-nitroso-diphenylamine	86-30-6	-	0.004
Total		10.9

*Maximum migration. Complete characterisation impossible due to coinciding peaks in TIC of the extract.

Table 7.3 Migration of selected nitrosamines – Balloon no. 6

	CAS-no.	Content mg/kg (%RSD)	Detection limit Mg/kg
N-nitroso-dimethylamine	62-75-9	0.02* (2)	0.004
N-nitroso-ethylmethylamine	10595-95-6	-	0.005
N-nitroso-diethylamine	55-18-5	-	0.004
N-nitroso-dipropylamine	621-64-7	-	0.005
N-nitroso-dibutylamine	924-16-3	0.006; 0.01**	0.004
N-nitroso-pyrrolidine	930-55-2	-	0.007
N-nitroso-morpholine	59-89-2	-	0.007
N-nitroso-piperidine	100-95-4	-	0.002
N-nitroso-diphenylamine	86-30-6	-	0.004
Total		0-0.03

* Maximum migration. Complete characterisation impossible due to coinciding peaks in TIC of extract.

** Maximum migration. Double determination differs more than 25%.

Table 7.4 Migration of selected nitrosatable compounds - balloon no. 6

	CAS-no.	Content mg/kg (%RSD)	Detection limit Mg/kg
N-nitroso-dimethylamine	62-75-9	2.7; 5.4 **	0.004
N-nitroso-ethylmethylamine	10595-95-6	-	0.005
N-nitroso-diethylamine	55-18-5	-	0.004
N-nitroso-dipropylamine	621-64-7	-	0.005
N-nitroso-dibutylamine	924-16-3	0.08; 0.12 ***	0.004
N-nitroso-pyrrolidine	930-55-2	-	0.007
N-nitroso-morpholine	59-89-2	-	0.007
N-nitroso-piperidine	100-95-4	-	0.002
N-nitroso-diphenylamine	86-30-6	-	0.004
Total		2.8-5.4

* Maximum migration. Complete characterisation impossible due to coinciding peaks in TIC of extract.

** Maximum migration. Double determination differs more than 25%.

*** Maximum migration. Double determination differs more than 25%.

Table 7.5 Migration of selected nitrosamines - Balloon no. 16

	CAS-no.	Content mg/kg (%RSD)	Detection limit mg/kg
N-nitroso-dimethylamine	62-75-9	0,02* (10)	0,004
N-nitroso-ethylmethylamine	10595-95-6	-	0,005
N-nitroso-diethylamine	55-18-5	-	0,004
N-nitroso-dipropylamine	621-64-7	-	0,005
N-nitroso-dibutylamine	924-16-3	0,02; 0,03**	0,004
N-nitroso-pyrrolidine	930-55-2	-	0,007
N-nitroso-morpholine	59-89-2	-	0,007
N-nitroso-piperidine	100-95-4	0,004* (0,5)	0,002
N-nitroso-diphenylamine	86-30-6	0,006; 0,009 ***	0,004
Total		0,03-0,04

* Maximum migration. Complete characterisation impossible due to coinciding peaks TIC of extract.

** Maximum migration. Double determination differs more than 25%.

*** Double determination differs more than 25%.

Table 7.6 Migration of selected nitrosatable compounds - balloon no. 16.

	CAS-nr.	Content mg/kg (%RSD)	Detection limit mg/kg
N-nitroso-dimethylamine	62-75-9	2.6 (13)	0.004
N-nitroso-ethylmethylamine	10595-95-6	-	0.005
N-nitroso-diethylamine	55-18-5	-	0.004
N-nitroso-dipropylamine	621-64-7	-	0.005
N-nitroso-dibutylamine	924-16-3	8.0 (7)	0.004
N-nitroso-pyrrolidine	930-55-2	-	0.007
N-nitroso-morpholine	59-89-2	-	0.007
N-nitroso-piperidine	100-95-4	-	0.002
N-nitroso-diphenylamine	86-30-6	-	0.004
Total		10.6

* Maximum migration. Complete characterisation impossible due to coinciding peaks in TIC of extract.

Table 7.7 Migration of selected nitrosamines - Balloon no. 20

	CAS-nr.	Content mg/kg (%RSD)	Detection limit mg/kg
N-nitroso-dimethylamine	62-75-9	-	0.004
N-nitroso-ethylmethylamine	10595-95-6	-	0.005
N-nitroso-diethylamine	55-18-5	-	0.004
N-nitroso-dipropylamine	621-64-7	-	0.005
N-nitroso-dibutylamine	924-16-3	-	0.004
N-nitroso-pyrrolidine	930-55-2	-	0.007
N-nitroso-morpholine	59-89-2	-	0.007
N-nitroso-piperidine	100-95-4	-	0.002
N-nitroso-diphenylamine	86-30-6	-	0.004
Total		-

Table 7.8 Migration of selected nitrosatable compounds - balloon no. 20

	CAS-nr.	Content mg/kg (%RSD)	Detection limit mg/kg
N-nitroso-dimethylamine	62-75-9	0,6 ; 1,3 **	0,004
N-nitroso-ethylmethylamine	10595-95-6	-	0,005
N-nitroso-diethylamine	55-18-5	-	0,004
N-nitroso-dipropylamine	621-64-7	-	0,005
N-nitroso-dibutylamine	924-16-3	0,2* (20)	0,004
N-nitroso-pyrrolidine	930-55-2	-	0,007
N-nitroso-morpholine	59-89-2	-	0,007
N-nitroso-piperidine	100-95-4	-	0,002
N-nitroso-diphenylamine	86-30-6	-	0,004
Total		0,6-1,5

* Maximum migration. Complete characterisation impossible due to coinciding peaks in TIC of extract.

Not unexpectedly N-nitrosodibutylamine and N-nitrosodimethylamine are the present nitrosamine types and the nitrosatable substances are likewise dominated by dibutylamine and dimethylamine.

A comparison of the results with the regulations on soothers and bottle teats shows that the balloons are violating these requirements significantly. Conversion of the total migration of nitrosamines and nitrosatable substances to µg/kg gives the grand totals stated in the table.

Table 7.9 Survey of total migration of nitrosamines and nitrosatable compounds in the selected balloons

Chemical class	Balloon no. 3 µg/kg	Balloon no. 6 µg/kg	Balloon no. 16 µg/kg	Balloon no. 20 µg/kg
Nitrosamines	80-110	0-30	30-40	< 7
Nitrosatable compounds	10,900	2,800-5,400	10,600	600-1,500

Table 7.9 shows that balloon no. 20 as to the nitrosamine complies with the requirement to soothers and bottle teats. This may also be the case for sample no. 6. Balloons nos. 3 and 16 exceed the limit value of 10 µg/kg for soothers and bottle teats. All four samples comply with the German regulations on balloons, i.e. a maximum content of 200 µg/kg (0.2 mg/kg). Balloons nos. 3, 6 and 6 do not fulfill the requirements to neither the maximum content of nitrosatable substances according to the limit values for soothers and bottle teats of 100 µg/kg nor the German requirements to 2,000 µg/kg (2 mg/kg).

At the same time it is assessed that the analysis method does not provide a correct value of the nitrosatable compounds at concentrations as high as they occur in balloons nos. 3 and 6, because of insufficient time for nitrosation of the amines. It can be seen that dibutylamine is still present in the chromatogram, although it is nitrosatable.

It should be mentioned that N-nitroso-diphenylamine, which has been detected in balloon no. 6, is used as retarder by vulcanisation of rubber (reducing the reaction velocity), but it is not likely that it is used by production of rubber products in Europe due to its harmful properties (X_nR22, R43, R51/53, S24, S36, S60, S61).

N-nitroso-piperidine may originate from the use of piperidine pentamethylene dithiocarbamate which will liberate piperidine at the vulcanisation temperature.