Grupo GUIA Departamento Química Analítica Universidad de ... · PDF fileGrupo GUIA, Departamento Química Analítica Universidad de Zaragoza TO the attention of Manuel Rodríguez,

Grupo GUIA, Departamento Química Analítica Universidad de Zaragoza TO the attention of Manuel Rodríguez,

ARAVEN

CERTIFICAT of COMPLIANCE

According to the Experimental Migration Tests carried out in the Polystyrene (PS), Polycarbonate (PC) and Polypropylene (PP) materials supplied by the Company ARAVEN, we can conclude that all the materials are in compliance with the EU legislation (Directive 2002/72 and its ammendements and RD866/2008 (Spain).

The experimental data found were:

Global Migration well below the established limit of 60 mg/Kg

Specific Migration, which included the volatile compounds, residual monomers, non volatile compounds (antioxidants, UV stabilizers, plastisizers, Bisphenol A) well below the SML established.

In all cases the migration tests were carried out in the four established food simulants under the standard conditions of 40ºC for 10 days.

Zaragoza, 2nd July, 2010

Prof. Dra. Cristina Nerín Catedrática de Universidad en Química Analítica Directora del Grupo GUIA Instituto de Investigación en Ingeniería de Aragón (I3A) Centro Politécnico Superior de Ingenieros (CPS) Depto. de Química Analítica Universidad de Zaragoza

Araven S.L.

Pol. Ind. Malpica C/E

50057 Zaragoza

España (Spain)

Zaragoza, October 7th, 2013

Conformity and quality declaration for ARAVEN products.

Every product included in HoReCa catalogue intended to be used in contact with food

(i.e. every product except for cleaning and waste products) is produced with steel, crystal,

PP, HDPE, LDPE, SAN, PC, PS, ABS o SILICONE suitable and approved for food contact,

according with the following regulations:

Subject EU Directive Date Spanish Law Date Comments

Traceability regulations

applicable to food

contact products

Reg.(CE) 1935/2004

Reg. (CE)19/2007 R.D. 866/08

Modificado por R.D. 103/2009

Reg. (CE) 10/2011 Modif. Reg.(CE)1183/2012

Reg. (CE) 1907/2006 (REACH)

Reg. (CE) 2023/2006 Modif. Reg. (CE) 282/2008

82/711/EU 23/10/1982

85/572/EU 31/12/1985 R.D. 1425/88 01/12/1988 modif.por Reg.(CE)19/2007

90/128/EU 21/03/1990

92/39/EU 23/06/1992 R.D. 2207/94 18/01/1995

93/8/EU 14/04/1993 R.D. 2207/94 18/01/1995 Modificado por R.D.2207/94

93/9/EU 14/04/1993

95/3/EU 23/02/1995 R.D. 510/96 21/04/1996 Modificado por R.D.2207/94

96/11/EU 12/03/1996 R.D. 1042/97 21/07/1997

97/48/EU 12/08/1997 R.D. 1752/98 06/08/1998

99/91/EU 01/12/1999 R.D. 442/2001 28/04/2001

02/72/EU R.D. 118/2003 Derogada por Reg (CE) 10/2011

08/39/EU R.D. 103/2009 Derogada por Reg (CE) 10/2011

Labeling, presentation

and publicity R.D. 1468/88 02/12/1988

Packaging and

wrapping R.D. 782/1998 30/04/1998

Technical sanitarian

regulation concerning

plastic material for

alimentary use

CONCLUSIONS.- According to the results of the tests, all ARAVEN tested materials (PP, PC and rubber) fulfil the EU legislation as food-contact materials.

Zaragoza, April 16th 2009

Prof. Dr. Cristina Nerín

Catedrática de Química Analítica Directora del grupo GUIA Directora del Master en Ingeniería del Medio Ambiente Instituto de Investigación en Ingeniería de Aragón (I3A) Centro Politécnico Superior de Ingenieros, Universidad de Zaragoza María de Luna 3, 50018 Zaragoza, España Tel: 34 976 761873; Fax: 34 976 762388

Grupo GUIA, Departamento Química Analítica

Universidad de Zaragoza

Global migration and specific migration test in food simulant D (olive oil) for ARAVEN

6th May 2011

Prof. Dra. Cristina Nerín de la Puerta

Grupo GUIA

I3A, CPS, Universidad de Zaragoza



2

Introduction Global and Specific Migration tests in the samples supplied by ARAVEN have been

carried out, following the European Regulation 10/2011/EU.

EXPERIMENTAL PROCEDURE

The following samples were received at the laboratory:

-‐ Polypropylene (PP) food container with polyethylene (PE) cap (white container)

-‐ Polycarbonate (PC) food container with PC cap (transparent container)

The migration tests were performed by filling the sample with the food simulant D

(olive oil). The samples were kept at 40 °C for 10 days. Blank tests were carried out on the

solution used for each series of migration tests. Three replicates were analyzed.

After the test, an aliquot of the simulant was taken and kept for the analysis.

Global migration

The global migration tests were performed following the experimental procedure

described in the Norm UNE 1186-‐8:2002.

The global migration value, M, was calculated according to the following equation:

M= [ma-‐mb-‐mc]/S

where:

M: global migration value in oil, mg/dm2

ma: initial weight of the sample, mg

mb: weight after the test, mg



3

mc: weight of the oil absorbed by the sample, mg

S: contact surface, dm2

Phthalate specific migration

Samples were analyzed by Solid Phase Microextraction (SPME), using a GC-‐MS

equipment. The compounds analyzed were: diethyl phthalate (DEP), dibutyl phthalate (DBP),

diisopropil phthalate (DiPP), diallyl phthalate (DAP), butyl benzyl phthalate (BBP) y di 2-‐

ethylhexyl phthalate (DEHP).

Standards from 0.225 to 40 mg/kg oil were prepared and analyzed. In the case of

DAP, the standards were from 0.010 to 40 mg/kg oil.

Antioxidant specific migration

Samples were analyzed by HPLC-‐UV. First, the standards were prepared in methanol

and then the oil was spiked with those standards. Finally, the oil samples were extracted with

methanol and this extract was analyzed by HPLC-‐UV.

The compounds analyzed were:

• Chimassorb 81

• Tinuvin P

• Irganox 1076

• Tinuvin 326

• Irgafos 168

• Cyasorb UV 5411

• BHT

• Tinuvin 327

• Irganox 1010



4

• Cyasorb UV 24

RESULTS

Global migration

Table 1 shows the results obtained in the samples.

Table 1. Global migration results (* Maximum limit: 10 mg/dm2).

M (mg/dm2)*

White container (PP) 2.97

White container cap (PE) 0.26

Transparent container (PC) 8.13

Transparent container cap (PC) 8.77

Phthalate specific migration

The analytical features found are shown in Table 2:

Table 2. Limits of quantification of phthalates in oil.

Compound LQ (mg/Kg oil)

DBP 0,213

DEP 0,231

DiPP 0,221

DEHP 0,229

BBP 0,230



5

DAP 0,010

For all the samples, none of the detected compounds are higher than the

corresponding limits of quantification.

Table 3 shows the specific migration limits according to the Directive 2007/19/EC and

Real Decreto 866/2008.

Table 3. Specific migration limits.

Compound SML (mg/Kg simulant)

DBP 0,3

DEHP 1,5

BBP 30

DAP Not detectable

Antioxidant specific migration

For all the samples, the detected signals are lower than the signal of a 2 ppm

standard. Table 4 shows the specific migration limits according to the Directive 2007/19/EC

and Real Decreto 866/2008.



6

Table 4. Specific migration limits.

Compound SML (mg/Kg simulant)

Tinuvin 326 30

Irganox 1076 6

Chimassorb 81 6

BHT 3

Tinuvin 327 30

Cyasorb UV24 6

CONCLUSIONS

According to the results obtained the articles under study can have the certificate of

compliance according to the Directive 2002/72/CEE, RD866/2008 and Regulation 10/2011/UE.

Zaragoza, 9th May 2011

Prof. Dra. Cristina Nerín Catedrática de Universidad en Química Analítica Directora del Grupo GUIA Instituto de Investigación en Ingeniería de Aragón (I3A) Centro Politécnico Superior de Ingenieros (CPS) Depto. de Química Analítica Universidad de Zaragoza

Grupo GUIA, Departamento Química Analítica Universidad de Zaragoza

GLOBAL and SPECIFICMIGRATION

OF POLYPROPYLENE ANDPOLYCARBONATE

CONTAINERS

ARAVENApril 2009


Catedrática de Química Analítica

Instituto de Investigación en Ingeniería de Aragón

Centro Politécnico Superior de Ingenieros



Description

According to the requirements of the Company ARAVEN, several PP and PCcontainers supplied by the Company were evaluated for being in direct contact withfood. The European Directives 72/2002/EC, 19/2007/EC, 39/2008/EC and the SpanishRD 866/2008 and 103/2009 were taken into account. The global and specific migrationtests were carried out on three independent replicates of each container and using thefollowing food stimulants:

1. Simulant A: Distilled water2. Simulant B: 3% (m/V) acetic acid in water3. Simulant C: 10 % (V/V) ethanol in water4. Simulant D:Isoctane and/or 95% (V/V) ethanol in water.

Antioxidants, plastisizers and other organic compounds present in the stimulants afterthe migration tests were analyzed.

The containers, caps and closure tights were also independently evaluated under thefollowing experimental conditions:

a) Global migration

The materials were placed in contact with each stimulant for 2 hours at 70ºC and thestimulant was evaporated to dryness after the test. The remaining residue wasgravimetrically analysed til constant weight.Blank samples were simultaneouslyanalyzed and the remaining residue was substracted from the final value obtained withthe samples.

b) Specific migration of Non volatile antioxidants, residual monomers and UVstabilizers

Non volatile antioxidants, residual monomers and UV stabilizers commonly present inthis type of plastics were analyzed by HPLC-UV at _=280 nm in each simulant after themigration test. The following standards were used for quantification:

• Chimassorb 81

• Tinuvin P

• Irganox 1076

• Tinuvin 326

• Irgafos 168

• Cyasorb UV 5411

• BHT


• Tinuvin 327

• Irganox 1010

• Cyasorb UV 24

• Bisfenol A (BPA)

And the detection limit was established at 2 mg/Kg. According to the legislation theSML established for Bisphenol A is 0.6 mg/Kg (See Table 1). Then, a GC-MSprocedure was also optimized and applied to the stimulants to evaluate the BPA with adetection limit of 0.48 mg/Kg.

Table 1.- Specific migration limits of some migrants.Compound SML (mg/Kg of simulant)

Tinuvin 326 30

Irganox 1076 6

Bisfenol A 0,6

Chimassorb 81 6

BHT 3

Tinuvin 327 30

Cyasorb UV24 6

c) Specific migration of terephthalic acid, isophthalic acid and diethylenglicol

According to the legislation the SML values are 3 0 , 5 y 7,5 respectively fordiethylenglicol, isophthalic acid and terephthalic acid. The simulants after the tests wereanalyzed by HPLC-MS. The detection limit was obtained at 0.5 mg/Kg in the stimulant.

d) Specific migration of plastisizers

Phthalates present in the simulants after the tests were also analyzed by Solid Phase

Microextraction (SPME) coupled to GC-MS. Diethylphthalate (DEP), dibutylphthalate (DBP)

and bis(2-ethylhexylphthalate (DEHP) were used as standards for quantitative purposes in therange from 0 to 1.24 mg/Kg in water (stimulant A) and the same using the other stimulants as


sample matrix for the calibration plots. Three independent replicates were analyzed. The

quantification limits obtained were 0.079 µg/g for DEP, 0.075 µg/g for DBP y 0.074 µg/g

for DEHP.

e) Screening of volatile compounds

A screening of volatile compounds was carried out by SPME-GC-MS in stimulant A tocheck the likely presence of other migrants.

f) Specific migration of butadiene

Butadiene was also analyzed by HS-GC-MS in the stimulants after the test. Thedetection limit was 0,016 mg/Kg ad the SML is 0.02 mg/Kg.


Results

Table 2 shows the results of global migration obtained .

Table 2.- Global Migration in the simulantsSAmple Simulant

A(µg/g)Simulant B

(µg/g)Simulant C

(µg/g)SimulantD (µg/g)

Polypropylene R1 < 0,01 < 0,01 < 0,01 < 0,01

R2 < 0,01 < 0,01 < 0,01 < 0,01

R3 < 0,01 < 0,01 < 0,01 < 0,01

R4 < 0,01 < 0,01 < 0,01 < 0,01

R5 < 0,01 < 0,01 < 0,01 < 0,01

Polycarbonate R1 < 0,01 < 0,01 < 0,01 < 0,01

R2 < 0,01 < 0,01 < 0,01 < 0,01

R3 < 0,01 < 0,01 < 0,01 < 0,01

R4 < 0,01 < 0,01 < 0,01 < 0,01

R5 < 0,01 < 0,01 < 0,01 < 0,01

The specific migration study showed in all cases values lower than 2 mg/Kg for theantioxidants and the stabilizer. In the case of BPA the signal obtained was in all cases30 times lower than that obtained for the standard of 0.48 mg/Kg.

The values obtained for diethylenglicol, isophthalic acid and terephthalic acid were inall cases lower than 0.5 mg/Kg.

Table 3 and 4 show the results of phthalates identified and quantified.


Table 3.- Phthalates obtained in Simulants A nd B.Sample Compound Simulant A

(mg/Kg)

Simulant B

(mg/Kg)

Polypropylene DEP < 0,079

DiBP < 0,075 < 0,075

DBP < 0,075 < 0,075

DEHP < 0,074 < 0,074

Polycarbonate DiBP < 0,075 < 0,075

DBP < 0,075 < 0,075

butyl-2-hexylphthalate - < 0,074

DEHP < 0,074 < 0,074

Table 4.- Phthalates obtained in Simulant CSample Compound Simulant C (mg/Kg)

Polypropylene DiBP < 0,075

DBP < 0,075

DEHP < 0,074

9 phthalates < 0,074

Polycarbonate DiBP < 0,075

DBP < 0,075

DEHP < 0,074

9 phthalates < 0,074

The SML values in the legislation are shown in Table 5.-


Table 5.- SML valuesCompound CAS number SML (mg/Kg in simulant)

bencilbutyl phthalate 85-68-7 30

bis(2-ethylhexylphthalate) 117-81-7 1,5

dibutylphthalate 84-74-2 0,3

Diésteres de ácido ftálico conalcoholes ramificados primarios,saturados C8-C10 más de 60%C9

68515-48-0 9

28553-12-0 9

68515-49-1 9

26761-40-0 9

In all cases the values obtained are well below the SML values.

The results obtained from the screening of volatile compounds is shown in Tables 6, 7.

Table 6.- Results of screening of volatile compounds in Simulant ASimulant A

Polypropylene Polycarbonate

Compound RT (min) Compound RT(min)

Fenol [96-76-4] 8,55 Fenol [96-76-4] 8,54

Fenol [140-66-9] 9,24 Fenol [140-66-9] 9,24

Ftalato de diisobutilo 10,86 Ftalato de diisobutilo 10,84

Ftalato de dibutilo 11,56 Ftalato de dibutilo 11,57

Adipato (ester) [103-23-1] 14,45 Ftalato de bis(2-etilhexilo) 15,64

Ftalato de bis(2-etilhexilo) 15,69 Indol (Skatole) [95-20-5] 16,42

Indol (Skatole) [95-20-5] 16,42


Table 7.- Results of screening of volatile compounds in Simulant BSimulant B


Compound RT(min) Compound RT (min)

Fenol [96-76-4] 8,53 Fenol [96-76-4] 8,53

Ftalato de dietilo 9,20 Ftalato de dietilo 9,17

Ftalato de diisobutilo 10,86 Fenol [140-66-9] 9,26

Ftalato de dibutilo 11,56 Ftalato de diisobutilo 10,85

Butil citrato 13,08 Ftalato de dibutilo 11,57

Butil citrato 13,52 Adipato (ester) [103-23-1] 14,45

Indol (Skatole) [95-20-5] 15,04 Indol (Skatole) [95-20-5] 15,04

Ftalato de bis(2-etilhexilo) 15,65 Ftalato de bis(2-etilhexilo) 15,63

Indol (Skatole) [95-20-5] 16,43 Indol (Skatole) [95-20-5] 16,42

Table 8.- Results of screening of volatile compounds in Simulant C


Simulante C


Compound RT(min) Compound RT (min)

Fenol [96-76-4] 8,57 Fenol [96-76-4] 8,53

Ftalato de diisobutilo 10,86 Fenol [140-66-9] 9,25

Ftalato de dibutilo 11,54 Ftalato de diisobutilo 10,85

Adipato (ester) [103-23-1] 14,46 Ftalato de dibutilo 11,54

Ftalato de bis(2-etilhexilo) 15,64 Palmitato de etilo (ester) [628-97-7]

12,93

Ftalatos (9) 17,3-18,2 Adipato (ester) [103-23-1] 14,45

Ftalato de bis(2-etilhexilo) 15,62

Indol (Skatole) [95-20-5] 16,42

Ftalatos (9) 17,3-18,2

In all cases the values obtained were in the order ng/g in the stimulant.

The analysis of Butadiene showed the values given in Table 9

Table 9.- Butadiene in the simulantsSimulant A

(mg/Kg in the simulant)

Butadiene < 0,016

Simulant B

Butadiene(mg/Kg in the simulant)

< 0,016


Simulant C

mg/Kg in the simulant

Butadiene <0,016

Simulant D

mg/Kg in the simulantButadiene <0,016

CONCLUSIONS

According to the results obtained the materials tested fullfil the EU legislation as foodcontact materials.

Zaragoza, 15th May, 2009.

Prof. Dr. Cristina NerínCatedrática de Química Analítica

Directora del grupo GUIAInstituto de Investigación en Ingeniería de Aragón (I3A)

Centro Politécnico Superior de IngenierosUniversidad de Zaragoza

María de Luna 3, 50018 Zaragoza, EspañaTel: 34 976 761873; Fax: 34 976 762388


GLOBAL and SPECIFIC

MIGRATION

OF POLYPROPYLENE,

POLYSTYRENE AND

POLYCARBONATE CONTAINERS

representative from glasses and

catering products

ARAVEN 1st July 2010



Instituto de Investigación en Ingeniería de Aragón




INTRODUCTION

According to the requirements of the Company ARAVEN, several PP, PS and PC

containers representative of glasses and catering products produced by ARAVEN were

supplied by the Company and were evaluated for being in direct contact with food. The

European Directives 72/2002/EC, 19/2007/EC, 39/2008/EC and the Spanish RD

866/2008 were taken into account. The global and specific migration tests were carried

out on three independent replicates of each container and using the following food

stimulants:

1. Simulant A: Distilled water 2. Simulant B: 3% (m/V) acetic acid in water 3. Simulant C: 10 % (V/V) ethanol in water 4. Simulant D:Isoctane and/or 95% (V/V) ethanol in water.

Antioxidants, plastisizers and other organic compounds present in the simulants after

the migration tests were analyzed.

a) Global migration

The materials were placed in contact with each simulant for 10 days at 40ºC and the

simulant was evaporated to dryness after the test. The remaining residue was

gravimetrically analysed til constant weight. Blank samples were simultaneously

analyzed and the remaining residue was substracted from the final value obtained with

the samples.

b) Specific migration of Non volatile antioxidants, residual monomers, UV stabilizers and volatile compounds

Non volatile antioxidants, residual monomers, UV stabilizers and volatile compounds

commonly present in this type of plastics were analyzed either by HPLC-UV, HPLC-

fuorescence or by GC-MS in each simulant after the migration test.

Bisfenol A (BPA) was analyzed by HPLC-fluorescence atexc = 250 nm y exc = 306 nm. The

mobile phase used was water and acetonitrile (50-50) in isocratic mode. And the detection limit

was established at 0.01 mg/Kg. According to the legislation the SML established for Bisphenol

A is 0.6 mg/Kg . Calibration plot was prepared from 0.01 to 5 mg/Kg.


c) Screening of volatile compounds

A screening of volatile compounds was carried out by SPME-GC-MS in all the

simulants to check the likely presence of other migrants.

RESULTS

THe following tables list the results of global migration in all the simulants.

Table 1. Global migration in simulant A.

sample Replicate Concentration (µµµµg/g)

sample A 1

2

3

<0,01

<0,01

<0,01

sample B 1

2

3

<0,01

<0,01

<0,01

sample C 1

2

3

<0,01

<0,01

<0,01

Table 2. Global migration in simulant B.


sample A 1

2

3

<0,01

<0,01

<0,01

sample B 1

2

<0,01

<0,01


3 <0,01

sample C 1

2

3

<0,01

<0,01

<0,01

Table 3. Global migration in simulant C.


sample A 1

2

3

<0,01

<0,01

<0,01

sample B 1

2

3

<0,01

<0,01

<0,01

sample C 1

2

3

<0,01

<0,01

<0,01

Tabla 4. Global migration in simulant D.


sample A 1

2

3

<0,01

<0,01

<0,01

sample B 1

2

3

<0,01

<0,01

<0,01

sample C 1

2

3

<0,01

<0,01

<0,01


SPECIFIC MIGRATION

DETERMINATION OF Antioxidants by HPLC-UV

11 Antioxidants were measured by HPLC-UV at λ between 254 and 400 nm. The mobile phase

used was wáter and methanol and the gradient 75-25% water-methanol for 5 minutes, to

reach 2-98% at 50 minutes and then constant for 30 min.

The compounds tested and their specific migration values are listed in the table5.

Table 5.- Specific migration limits of some migrants.

Compound SML (mg/Kg of simulant)

CHIMASSORB 81 6

CYASORB UV 24 6

CYASORB UV 5411 Without limit

IRGAFOS 38 5

IRGAFOS P-EPQ 18

IRGANOX 1010 Without limit

IRGANOX 1076 6

TINUVIN 326 30

TINUVIN 327 30

TINUVIN P 30

BHT 3

None of the compounds were found in the simulants at concentration higher than 2 mg/Kg, in

any of the replicates and materials tested.


DETERMINATION OF BISPHENOL A

The table 6lists the analytical features of BPA.

Table 6.- Analytical features of BPA analysis Compound Lineal range (R

2) LOD (ng g

-1) LOQ (ng g

-1)

BPA 0,1 – 9,93 (µµµµg g-1

) 0,9999

BPAa 8,29 – 63,80 (ng g

-1) 0,9999 20 70

a Calibration plot in a lower concentration range to obtain the LOD and LOQ values (Compañó, Ríos 2002).

None of the samples gave a value higher than 0,02 mg/Kg in any of the simulants

tested.

SCREENING OF Volatile Compounds

The following Tables 7 & 8 give the SML established and the values obtained in the

samples respectively.


Table 7.- SML of phthalates according to directive 2007/19/EC and Real Decreto 866/2008.

Compound CAS SML (µg/g de simulant)

Ftalato de bis(2-etilhexilo) DEHA 117-81-7 1,5

Ftalato de dibutilo (DBP) 84-74-2 0,3

Diésteres de ácido ftálico con

alcoholes ramificados primarios,

saturados C8-C10 más de 60% C9

68515-48-0 9

di-''isononyl'' phthalate 28553-12-0 9

68515-49-1 9

Diisodecyl phthalate 26761-40-0 9

Tabla 8. Screening of volatiles in simulant A.

sample Compound [CAS] Concentration (mg/Kg)

Muestra A Ftalato de bis(2-etilhexilo) (117-81-7)

DBP (84-74-2)

Diisodecyl phthalate (26761-40-0)

0,075

0,098

1,023

Muestra B Estireno (100-42-5)

DBP (84-74-2)

DEHA (117-81-7)

1,543

0,087

0,253

Muestra C DBP (84-74-2)

DEHA (117-81-7)

0,087

0,386

68515-49-1 1,524

Diisodecyl phthalate (26761-40-0) 0,964

In all simulants the concentration values found were similar as well as the compounds.


CONCLUSIONS

In all cases the values obtained are below the SML values. According to the results

obtained the materials tested are in compliance with the EU legislation as food contact

materials.

Zaragoza, 1st July, 2010.

Prof. Dr. Cristina Nerín


Directora del grupo GUIA

Instituto de Investigación en Ingeniería de Aragón (I3A)



María de Luna 3, 50018 Zaragoza, España

Tel: 34 976 761873; Fax: 34 976 762388

Documents

Grupo GUIA Departamento Química Analítica Universidad de ... · PDF fileGrupo GUIA, Departamento Química Analítica Universidad de Zaragoza TO the attention of Manuel Rodríguez,