Open Access

Phthalates in soft PVC products used in food production equipment and in other food contact materials on the Danish and the Nordic Market 2013-2014

International Journal of Food Contamination20163:3

DOI: 10.1186/s40550-016-0026-6

Received: 2 December 2015

Accepted: 3 March 2016

Published: 9 March 2016

Abstract

Background

Food contact materials (FCM) containing phthalates can be a source of food contamination when used in plastics for food production equipment, in utensils for food contact and in packaging. Since 2008 several of the phthalates used for FCM were regulated in the EU; some of them because they were well-known endocrine disruptors. Results of the Danish Food Authorities control in 2008 and 2009 showed 23 % non-compliant samples. Critical FCMs turned out to be those made from plasticised PVC and sold as suitable for contact with fatty foodstuffs. Targeted follow up control campaigns were therefore arranged by the Danish food authorities (latest in 2013) and by the Nordic food authorities in a common campaign in 2014.

Findings

FCM plastics were analysed for phthalate content and when needed additionally tested for migration of phthalates according to the declared area of use with respect to food type, contact temperature and time in contact with food. In both recent control campaigns about 1/3 of the samples analysed exceeded the current maximum limits for phthalates (especially DBP and DEHP) in plastics or showed migration into the fatty food simulant above the specific migration limits. Critical sample types were conveyor belts, hoses and gloves.

Conclusions

Legal limits for phthalates were exceeded in many of the samples analysed in recent tests, including a large proportion of conveyor belts and gloves. The proportion of non-compliant conveyor belts, hoses and gaskets was lower in 2013 and 2014 than in 2008-2009, whereas the proportion of non-compliant gloves increased.

Keywords

Food Contact Materials (FCM) Official control Phthalate Migration DEHP DBP DiNP DiBP

Findings

This paper contains a collection of results from two targeted enforcement campaigns in 2013 and 2015, planned and carried out together with the Food Authorities in Denmark (Holm et al. 2013) and in the other Nordic Countries (Li et al. 2015), respectively. The Food Authorities were responsible for sampling of Food Contact Materials (FCM) and collecting documentation of compliance (DoC). The National Food Institute was responsible for the analytical work and migration tests. Similar campaigns were conducted in Denmark in 2008 and 2009 and it was expected to see a reduced number of non-compliances with the regulation.

Legislation

Since 2008, plastic FCM’s in the EU market shall comply with the restrictions and specifications for the following phthalates: Dibutyl phthalate (DBP), Butylbenzyl phthalate (BBP), Di- (2-ethylhexyl) phthalate (DEHP), Di-isononylphthalate (DiNP) and Di-isodecylphthalate (DiDP). In some cases, the phthalates used in FCM are regulated by maximum permitted residual contents (weight % concentration in the FCM, here referred to as Quantum maximum, Qm) and in others by SML’s, Specific Migration Limits (mg/kg food simulant). The interpretation of the restrictions is not straight forward and is presented in more detail in a guideline from the EU reference laboratory (EURL) for FCM (Hoekstra et al. 2011) where a table of the critical parameters to control in enforcement is shown (Table 1). Control of the migration limits for phthalates was performed with the official food simulant for FCM in contact with fatty foods according to the Plastics Regulation (EU) No 10/2011 (EU, 2011).
Table 1

Clarification of the critical parameter of “classical” phthalates for control in enforcement work (adapted and slightly simplified from Hoekstra et al. 2011)

PM-no

Substance

SML

Qm

Parameter to control in single use Food Contact Material *

Parameter to control in repeated use Food Contact Materials

  

mg/kg food simulant

% in plastic

Fatty food

Infant food

Non-fatty food

Fatty food

Infant food (non-fatty)

Non-fatty food

74640

Phthalic acid, bis(2-ethylhexyl)ester (DEHP)

1.5

0.1

Qm

Qm

SML

74880

Phthalic acid, dibutyl ester (DBP)

0.3

0.05 #

Qm

Qm

SML

74560

Phthalic acid, benzyl butyl ester (BBP)

30

0.1

Qm

SML

SML

75100

Phthalic acid, diester with C8-C10 (DiNP)

9 $

0.1

Qm

SML(T)

SML(T)

75105

Phthalic acid, diester with C9-C11 (DiDP)

9 $

0.1

Qm

SML(T)

SML(T)

* Packaging made from glasses with lid containing a plasticized gasket is usually considered as a single use material; # only permitted in polyolefins; $ SML(T) is sum of DiNP and DiDP

Qm, maximum permitted quantity of the residual substance in the material; SML, specific migration limit

In the two recent control campaigns official food inspectors were asked to take samples of soft FCM plastics, which either were claimed by the producer, importer or retailer to be suitable for contact with fatty foodstuffs or which were found by inspections to be used for this purpose in the food industry. Detailed instructions were given with respect to sample types, number and size of items. Before selling their product on the European market, producers and importers of plastic FCM’s are obliged to fill out a DoC claiming compliance with the EU regulation among other requirements stating any restrictions in the legal area of use for the final FCM. Information about acceptable time and temperature-range in use as well as limitations, if any, of food types in contact with the FCM are among the most important parameters. Such information is needed when the official control laboratory decides how to test the plastic material for compliance with the legal limits in the plastic and in the food simulant.

Analytical Strategy

The accredited analysis of the above five phthalates in our laboratory was described earlier in details by Petersen and Jensen (2010). In brief the following strategy was applied: the FCM was first analysed with infrared spectroscopy to verify that the sample was a plastic material. If not, the sample was discarded. Secondly, the phthalate concentration in the plastic was determined by dissolution/precipitation (e.g., PVC) or extensive extraction of the polymer (e.g., polyolefins) followed by analyses of the extract using gas chromatography with mass selective detection (GC-MSD). The sample was deemed acceptable if all phthalates were below the Qm-limits. If the phthalate concentration exceeded the Qm, the use intended by the supplier and the real use were checked to conclude on whether or not the FCM was compliant (Table 1). If so, no further testing was performed and the sample was deemed non-compliant. If the sample complied with Qm-limits but contained phthalates, migration tests were performed according to EU 10/2011, Annex V, with the food simulant olive oil or 50 % ethanol taking any restrictions mentioned in the DoC for contact time and temperature into consideration (EU 2011). The oil was analysed using the EURL-method of Bratinova et al. (2010). Phthalates in 50 % ethanol were transferred to an organic solvent using liquid/liquid extraction after dilution of the simulant with water. After testing the sample in one test (single use FCM’s) or three times in a single sided test with new portions of food simulant (repeated use FCM’s) it was concluded if the sample complied with the SML’s or not. In Table 3 sample characteristics, type of test applied and result of the analysis is shown for each individual sample.

Results and discussion

In Table 2 results from the recent control campaigns are compared with results from the FCM control in 2008/2009 (Petersen and Jensen, 2010). The overall picture shows that the non-compliant FCM’s belong to only a few sample types: food production equipment containing PVC like conveyor belts, hoses and gloves for single or repeated use. In these categories there continue to be a high proportion of illegal products on the market. In contrast, problems with high amounts of phthalates plasticisers in the gasket of screw caps for glass containers seen in 2008/2009 seems to be solved. However, it was reported that there are other problems with migration of substances substituting phthalates as primary plasticisers (McCombie et al. 2015). Samples of PVC cling film did not contain any of the five phthalate plasticisers.
Table 2

Survey of results from three control campaigns about phthalates in food contact plastics. Total number of samples analysed in different types of FCM and the frequency of violations

Type of food contact material

Danish control 2008/2009 **)

Danish control 2013 ***)

Nordic control 2014 ****)

Samples analysed

Non-compliances No./%

Type of violation (Qm/SML)

Samples analysed

Non-compliances No./%

Type of violation (Qm/SML)

Samples analysed

Non-compliances No./%

Type of violation (Qm/SML)

Conveyor belt

6

6/100

6/0

12

8/67

4/4

3

2/67

1/1

Hose

5

4/80

4/0

7

2/29

1/1

3

1/33

1/0

Gloves

20

5/25

5/0

5

2/40

2/0

3

3/100

3/0

Gasket in screw cap/lid

28

8/33

8/0

6

0

0/0

4

0/0

0/0

Various sample types *)

41

0/0

0/0

1

0

0/0

6

0/0

0/0

Total

100

23/23

 

31

12/39

 

19

6/32

 

*) plastic film, cling film, bottles, containers, cutlery, kitchen and tableware

**) Petersen and Jensen, 2010; ***) Holm et al., 2013; ****) Li et al. 2015

For conveyor belts typical problems were a high concentration of DiNP and/or DiDP in the PVC plastic layers leading to a high migration into fatty foods. Many belts contained also DBP or DEHP in the plastic in amounts below 1 % but above the Qm-limits, presumably because they are used as a production aid in an inner adhesive layer. It was shown earlier that phthalates readily diffuse into the food contact layers after production of the laminated conveyor belt since it contained no functional barrier against migration (Petersen and Jensen, 2010). The non-compliant PVC-hose from 2014 contained DEHP as the primary plasticiser. It could be expected that DEHP would have been substituted with the less toxic DiNP or DiDP, which was the case in the 2013 campaign where one PVC hose contained DiDP as primary plasticiser.

Suppliers of food production equipment like conveyor belts and hoses are reluctant to set restrictions for the legal area of use for their products. If needed, the DoC should state to the user of the FCM that it is not suitable for direct contact with fatty foodstuffs. Clear statements of the maximum temperature and contact time for safe use of the FCM is needed. However, in many cases the food inspectors did not find any relevant documentation, when they took the samples (Table 3). Annex 5 in the plastics regulation (EU 2011) says that: “verification of compliance of migration into foods with the migration limits shall be carried out under the most extreme conditions of time and temperature foreseeable in actual use”. For hoses and conveyor belts there is a risk that the contact time with food can be quite long in the case there are minor stops in the production, and the FCM must be tested accordingly. Food is considered to be the primary source of human intake of phthalates like DBP and DEHP and food production equipment is a potential source of such food contamination. Many of our foodstuffs contain relatively low levels of DEHP, a substance which has a rather low tolerable intake per kg bodyweight (TDI). Because of the high intake of food per kg bodyweight for small children it could be shown e.g., by Fierens et al. (2012) that the DEHP exposure can be close to the TDI. Since endocrine disruptors like DEHP and DBP easily can be substituted with other less toxic substances, there is no reason to use them in such critical applications.
Table 3

Detailed sample data and test results from enforcement campaigns in 2013 (Denmark) and 2014 (Nordic Countries)

   

Concentration in the plastic (%)

Limitations in use (from suppliers DoC etc.)

Test conditions (laboratorys assessment)

Reduction factor D2 applied

Results, migration into food simulant (mg/kg)

Sample no. (13-x = DK; 14-x = Nordic)

Country of origin

Sampling Type

DBP

BBP

DEHP

DiNP

DiDP

Foods excluded

Max Time (hours)

Max Temperature (°C)

Food Simulant

Time (hours)

Temperature (°C)

DEHP

DiNP

DiDP

13-13

 

Bag in Box

<0.02

<0.02

<0.01

<0.03

<0.03

          

13-1

Germany

Conveyor belt

   

high content

  

0,25

40

oil

0,5

40

3

 

17.8 (12.8-22.0-18.5)

 

13-5

 

Conveyor belt

   

high content

  

short

100

oil

0,5

70

3

 

6.6 (5.7-7.7-6.2)

 

13-12

 

Conveyor belt

   

high content

    

oil

0,5

70

3

 

30 (30.8-31.7-26.7)

 

13-21

 

Conveyor belt

<0.02

<0.02

<0.01

<0.03

<0.03

          

13-22

 

Conveyor belt

<0.02

<0.02

<0.01

<0.03

<0.03

some fatty

2

70

       

13-23

 

Conveyor belt

  

0,026

high content

  

2

40

oil

2

40

3

 

9.1 (9.1-9.5-8.7) #

 

13-24

 

Conveyor belt

0.26 (0.27-0.27-0.25)

<0.02

<0.01

high content

           

13-25

 

Conveyor belt

<0.02

<0.02

0.52 (0.50-0.63-0.42)

high content

           

13-26

 

Conveyor belt

0.78 (0.50-0.96-0.89)

<0.02

<0.01

high content

3.7

          

13-27

 

Conveyor belt

<0.02

 

<0.01

high content$

   

70

       

13-28

 

Conveyor belt

   

>0.1 %

   

70

oil

0.5

70

3

 

28 (25.3-26.4-33.3)

 

13-29

 

Conveyor belt

<0.02

high content

0.25

high content

           

13-2

 

Gasket in Lid

<0.02

<0.02

<0.01

<0.03

<0.03

          

13-3

 

Gasket in Lid

<0.02

<0.02

<0.01

<0.03

<0.03

          

13-4

 

Gasket in Lid

<0.02

<0.02

<0.01

<0.03

<0.03

          

13-11

Germany

Gasket in Lid

<0.02

<0.02

<0.01

<0.03

<0.03

          

13-19

Italy

Gasket in Lid

<0.02

<0.02

<0.01

<0.03

<0.03

 

1

100

       

13-20

Czech Republic

Gasket in Lid

<0.02

<0.02

<0.01

<0.03

<0.03

          

13-15

Thailand

Gloves, repeated use

<0.02

<0.02

<0.01

<0.03

<0.03

          

13-16

Japan

Gloves, repeated use

<0.02

<0.02

<0.01

<0.03

<0.03

          

13-17

Monaco

Gloves, repeated use

   

detected

 

fatty

  

50 % EtOH

2

40

  

<0.33

 

13-9

 

Gloves, single use

<0.02

<0.02

<0.01

13.9¤

<0.03

fatty

         

13-30

China

Gloves, single use

<0.02

<0.02

<0.01

>0.1 %

3.0 (3.3-3.4-2.3)¤

          

13-10

 

Hose

    

25.7 (27.3-24.7-25.0)

fatty

 

60

50 % EtOH

2

60

   

95 (97.8-98.4-87.7)

13-14

Turkey

Hose

<0.02

<0.02

0.62 (0.54-0.68-0.64)§

<0.03

<0.03

fatty

         

13-18

Ireland

Hose

<0.02

<0.02

<0.01

<0.03

<0.03

          

13-31

France

Hose

<0.02

<0.02

<0.01

<0.03

<0.03

  

60

       

13-6

 

Milk hose

<0.02

<0.02

<0.01

detected

<0.03

   

50 % EtOH

0.5

40

  

<0.33

 

13-7

 

Milk hose

<0.02

 

‘0.04

<0.03

<0.03

          

13-8

 

Milk hose

<0.02

<0.02

<0.01

<0.03

<0.03

          

14-2

Italy

Conveyor belt

0.28

<0.02

<0.01

high content

<0.03

 

2

80

       

14-3

Germany

Conveyor belt

<0.02

<0.02

<0.01

high content

<0.03

 

short term

90

oil

0.5

70

3

 

27 (27-25-28)

 

14-13

 

Conveyor belt

<0.02

<0.02

<0.01

<0.03

<0.03

          

14-7

Germany

Gasket in Lid

<0.02

<0.02

<0.01

<0.03

<0.03

  

121

       

14-10

France

Gasket in Lid

<0.02

<0.02

<0.01

<0.03

<0.03

 

1

100

       

14-16

Italy

Gasket in Lid

<0.02

<0.02

<0.01

<0.03

<0.03

fatty

1

100

       

14-18

Italy

Gasket in Lid for wine

<0.02

<0.02

<0.01

<0.03

<0.03

          

14-14

Taiwan

Gloves, repeated use

<0.02

<0.02

28.2 (30.8-24.6-29.2)

<0.03

<0.03

          

14-5

China

Gloves, single use

<0.02

<0.02

<0.01

34

<0.03

fatty*

         

14-15

Taiwan

Gloves, single use

<0.02

<0.02

<0.01

43

<0.03

fatty

         

14-6

Italy

Hose

<0.02

<0.02

0,08

max 0,1 %

<0.03

 

2

40

oil

2

40

 

<0.3 (3x < 0.3)

  

14-8

Finland

Hose

<0.02

<0.02

<0.01

<0.03

<0.03

 

1

40

       

14-19

 

Hose

<0.02

<0.02

25.8 (25.9-24.3-27.3)

<0.03

<0.03

None

 

60

       

14-1

Finland

Polyolefin film

<0.02

<0.02

<0.01

<0.03

<0.03

 

0.5

85

       

14-4

France

PVC cling film

<0.02

<0.02

<0.01

<0.03

<0.03

 

0.25

100

       

14-9

Finland

PVC cling film

<0.02

<0.02

<0.01

<0.03

<0.03

pure fats

 

40

       

14-11

Germany

PVC cling film

<0.02

<0.02

<0.01

<0.03

<0.03

Food with D2 < 4

0.25

100

       

14-12

Germany

PVC cling film

<0.02

<0.02

<0.01

<0.03

<0.03

          

14-17

Italy

PVC cling film

<0.02

<0.02

<0.01

<0.03

<0.03

 

2

70

       

Results shown in bold are above the legal limits

*In practice used in contact with fatty food, although this was not recommended by the supplier

$ Production stopped

§ Declared as phthalate free hoses

¤ Qm value for infant food violated

# Non-significant violation of the migration limit

With respect to gloves the situation remains very unsatisfactory. It was shown years ago that use of DEHP plasticised gloves in catering could lead to an increased intake of DEHP e.g., for patients in hospitals (Tsumura et al. 2003). Single use PVC gloves, often in 100 pcs boxes, are cheap and frequently used but have a very high content of plasticiser. DEHP-plasticised gloves are still on the market without statements in the DoC and on the packaging, that they are unsuitable for contact with infants foods and fatty foods. In one case the gloves were labelled correctly but used in catering for fatty foods.

In the 2008/2009 campaign the food inspectors were asked to sample all kind of plastic samples provided they were claimed to be suitable for fatty food contact. It transpired that all findings of phthalates were in PVC plastics and in the following campaigns inspectors were urged to concentrate sampling on this type of polymer. However, over the whole period a total of 48 samples made from polymers other than PVC were analysed and in no case were phthalates present.

Conclusions

The overall conclusion from the control is that with 23 to 39 % non-compliant samples in the recent campaigns there is still a lot of room for improvement. Importers and producers must be better at compiling the DoC correctly to guide the users of the FCM to avoid excessive migration of endocrine disruptors like phthalates – which could easily be replaced with less toxic substances. Findings of phthalates in plastic FCM was often connected to the polymer PVC. Plasticised PVC and phthalates is a problematic cocktail, when used in contact with fatty foods.

Declarations

Open AccessThis article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.

Authors’ Affiliations

(1)
Danmarks Tekniske Universitet

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Copyright

© Petersen and Jensen. 2016