Resolution Metals and Alloys of the Council of Europe Resolution metals and alloys (adopted june...

Resolution Metals and Alloys of the Council of

Europe

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Dr. Ing. Fabien Bolle

[email protected]

15th october 2015

Preamble : The Council of Europe

The Council of Europe (Strasbourg), is the

vastest and most senior of the

European political organizations.

Created in 1949 by 10 States founders, it covers the near total of the European continent today, with its 47

Member States (800 million Europeans) .

2

•États fondateurs

•Autres pays membres

•États observateurs à l’Assemblée parlementaire

•États observateurs au Comité des Ministres

•États candidats officiels

The Council of Europe is the first

organization to have legislated in

many fields, like those on the

prohibition of the cloning of human

beings or on the repression of

terrorism… or of resolutions on

materials in contact with the

foodstuffs

In 2008, the Committee of the Ministers dissolved this partial Agreement and transferred its activities related to the

cosmetics and materials for food packaging and medicines to the European Directorate for Quality of Medicine, or

DEQM (37 Member States).

3

Ctee for the Protection of

Human Health (CD-P-SC)

Ctee of Experts packaging

Food & pharma

Ctee of Experts

cosmetics

Representatives of the members

states (parties to the Convention on the

development of EU Pharmacopeia with

competences in national programs for the

protection of consumers’ health)

Experts appointed by MS (also

from Industry)

Ad Hoc WG

Ad Hoc WG

Ad Hoc WG

+ Cooperation with European

Commission, JRC and EFSA

Revision of texts under the aegis of the EDQM :

work by country rapporteur (Example : Belgium for metals and alloys, Germany for paper and board… )

Comitee of ministers

Ad Hoc WG

Ad Hoc WG

Ad Hoc WG

• Texts of the Council of Europe

1. Resolutions (adopted by the Committee of Ministers)

2. Guidelines and/or Technical Documents (TD) adopted by

“Steering Committee”

• These documents may require a total or partial transposition in the

national law to become binding.

• However,…

• In the absence of EU Regulation, the documents of the Council of Europe can be used as harmonized reference documents to show the harmlessness and the inertia of a FCM (art. 3 of the EU Regulation)

• In any cases, a resolution has a strong harmonized interpretative value because, it receives political approval by the governments of all member states.

!

4

EC specific texts :

84/500 ceramics

10/2011 plastics…

Transpositions in

national texts

Resolutions and

guidelines of

CoE

(Strasbourg)

Interpretation of Article 3

for matters

not covered by specific

EU legislation

“Complementarity of the fo

ur international

bodies”

EFSA JRC

Harmonized legislation(s) :

5

Interest of the work of the CoE

Many materials are not the object of specific texts

of the European Union

These non considered materials are often covered by a resolution of the

Council of Europe

There are more and more national initiatives following the many crises in

the “non-plastics” (Inks: Swiss Ordinance, varnish Belgian Decree,

revision in the Netherlands, BfR revision of the recommendations…) :

Lack of up to date texts is detrimental for :

• Consumer mutual recognition the lower standard is

favoured

• Industry : very difficult to implement different norms in different

countries

6

Important results of CoE this last years

1) Resolution metals and alloys (adopted june 2013): complete

document with limits, new practical concepts, harmonized view of

assessment agencies, new methods (simulants, SRL,…)… now applied in

some countries by industry and authorities… Ljubljana : Symposium

on the metals and alloys Resolution (6 and 7 november 2014)

2) Establishment of a database of substances known by members states of

CoE and used in FCM with toxicological evaluation by software (more

than 10 000 substances) : free access for members states and

subscription for companies Expert Committee of CoE to supervise

this work (coming from a belgian initiative)

3) Participation of UE instances : JRC, EFSA,… invitation of CoE at EU

experts comitees… (Initiatives are being taken to increase the

participation of member states of the EU at meetings of CoE)

7

The SRL

The guidelines

1. New simulants

2. New concept for repeated use

3. Problem of measurment of utensils

Conclusion

Resolution Metals and Alloys of the

Council of Europe :

Innovative approach to product testing

I. The SRL vs SML

a) Release vs migration : electrochemical influence

of O2, simultaneus use of 2or more metals than

pile effect, passivation…

b) No Diffusion

c) In definition of SRL : metals are all ubiquitaires

(than the Exception phtalates : is the rue in

metals)

d) Use of allocation factor or ALARA (taking into

account situation as is)

9

• Classical migration : diffusion (plastics,…)

• Ceramics, enamelled cast iron : releases

(diffusion limited dissolution)

• Release from metals and alloys : electrochemical

10

Different types of releases :

Example of multi exposure : Aluminium

Exposure adult of 60 kg Al (mg)

Food Adult median (60 kg) 1.8

Food Adult de 60 kg (p95) 4.7

Drinking water Mediane 0.027

Drinking water au P90 0.091

Ingestion Dust/soil mediane 10 mg/jour (71/29) 0.30

Ingestion Dust/soil RME 20 mg/jour (71/29) 0.60

Inhalation (Adult mediane) (16,7 m³/Day) 0.0017

Inhalation (Adult RME) (22,6 m³/Day) 0.020

Food contact Median 0.18

Food contact P95 0.49

Sum for median Scenario (mg/Day) 2.31

Sum for RME Scenario (mg/Day) 5.90

TVR (TDI inn mg/Day) 8.6

% TRV : scenario median 26.9 %

% TRV : scenario RME 68.6 %

Different concepts uses in definition of an SRL

Criteria

Appropriate

toxicological

reference value

Appropriate oral

exposure estimate

Proportion of

toxicological

reference value

allocated to

metallic FCM

Comment

1 Yes Yes Variable

Allowance fills the gap between worst-case oral

intake and the toxicological reference values (e.g.

copper, molybdenum & zinc)

2 Yes

Yes, but exceeds

toxicological

reference value

ALARA or if no

data available 10% (e.g. aluminum)

3 Yes No 20%

(e.g. silver, cobalt, manganese & nickel) Allowance

is in agreement with the WHO “Drinking Water

Guidelines”

4 No Yes Not applicable

Since no toxicological reference value is available, an

SRL was derived from intake data. (e.g. chromium,

iron & vanadium)

5 Yes Not applicable 10%

Only applicable for impurities. Independent of oral

intake, for impurities a general allowance of 10% is

applied

6 Not applicable Not applicable Not applicable Setting of a SRL was considered as not necessary

(e.g. magnesium & titanium)

SRL and transient SRL (3 years)

Symb

ol

Name SRL

[mg/kg

food]

Maximum tolerable

concentration during

transitional period

(f: multiplication factor)

Ag Silver 0.08

Al Aluminium 5

Co Cobalt 0.02 0.1 (f=5)

Cr Chromium 0.250 1.0 (f=4)

Cu Copper 4

Fe Iron 40

Mg Magnesium -

Mn Manganese 1.8

Mo Molybdenum 0.12 0.6 (f=5)

Ni Nickel 0.14 0.7 (f=5)

Sn* Tin 100

Ti Titanium -

V Vanadium 0.01 0.05 (f=5)

Zn Zinc 5

For the transposition of quality specifications described in the Guide into national legislation, the Committee

recommended that transitional periods be considered by national authorities.

During the transitional period (3 years), a tolerable deviation from the SRL for certain metallic elements

could be indicated.

Symbol Name SRL

[mg/kg

food]

Maximum tolerable

concentration during

transitional period

(f: multiplication factor)

As Arsenic 0.002 0.01 (f=5)

Ba Barium 1.2

Be Beryllium 0.01 0.05 (f=5)

Cd Cadmium 0.005 0.02 (f=4)

Hg Mercury 0.003 0.015 (f=5)

Li Lithium 0.048

Pb Lead 0.010 0.04 (f=4)

Sb Antimony 0.04 0.2 (f=5)

Tl Thallium 0.0001 0.0005 (f=5)

The SRL

The guidelines

1. New simulants



Conclusion

Resolution on Metal and Alloys

of the Council of Europe

New concepts :

1. New simulants : citric acid, artificial tap water…

2. Double limits for repeated use

3. New methodology of measurment of utensils

The guidelines : Chapter 3 Analytical methods

The SRL

The guidelines

1. New simulants



Conclusion



1. New simulants

a) Artificial Tap water :

DIN 10531 (2011-06) Food hygiene - Production and dispense of hot beverages from hot beverage appliances - Hygiene requirements, migration test.

Ion concentrations: calcium 16.4 mg/L, magnesium 3.3 mg/L, sodium 16 mg/L, hydrogen carbonate 44 mg/L, chloride 28.4 mg/L, sulfate 13 mg/L.

More realistic than distillated water

b) Citric Acid :

more realistic than acetic acid for some reasons

The reasons of the

choice and change

supported by CoE

a) ATW : release in Distilled Water vs ATW

18

-50,0

0,0

50,0

100,0

150,0

200,0

250,0

300,0

0 200 400 600 800 1000 1200 1400 1600

Rele

ase i

n µ

g/d

m²

Time in min.

Release of Nickel form Nickel-plated pieces in Water MQW and ATW at 20 °C, 40°C and 70°C

MQW 20 °C

MQW 40 °C

ATW 20 °C

ATW 40 °C

Distilled Water underestimates the releases for this case at 20°C and

40°C. And, in any cases, nobody drinks distilled water …

b) Choice of acid simulant

1. Choice of acetic acid was conventional : One of the rational was that acetic acid permits

determination of global migration by evaporation/gravimetry

Other experts invoque the common use of this acid…

2. As release in metals and alloys is

electrochemical the nature of acid is prevalent Example : for aluminium with acetic acid the results are

totally unrealistics… (Dissolution of the material)

19

Ad hoc group work

on choice of simulant

First reasoning : Next composition table of Souci et al. ( Food Composition

and Nutrition Tables 2000 SW Souci, W Fachmann,H Kraut

mbH, Stuttgart 2000 1182 pp (English, German, French)) .

20

Acid Acetic Butyric Citric Lactic Malic Oxalic

average (mg/kg) 2,4 89,5 46,4 41,3 39,8 3,5

minimum (mg/kg) 0,35 12 1,19 0,3 0,55 0

maximum (mg/kg) 7,7 260 492 121 569 44,2

Food containing acid 4 6 29 12 26 21

pKa 4,76 4,86 3,13 3,86 3,46 1,25

pH at average [ ] 4,58 3,93 3,37 3,6 3,49 2,83

pH at maximum [ ] 4,33 3,69 2,86 3,37 2,92 2,28

Total of considered food

(with acid content 106 106 106 106 106 106

Second reasoning : What is the typic acidity in food ?

Under pH 4.5 :

only fruits

and

vegetables

(excepted

vinegar)

4,5

Simul. B

2,5

Apples Malic, quinic, aketoglutaric, oxalacetic, citric, pyruvic, fumaric, lactic and

succinic acids

Apricots Malic and Citric acids

Avocados Tartaric Acid

Bananas Malic, citric, tartaric and traces of acetic and formic acids

Bilberry Citric

Blackberries Isocitric, Malic, lactoisocitric, shikimic, quinic, and traces of citric

and oxalic acids

Blueberries Citric, malic, glyceric, citramalic, glycolic, succinic, glucuronic,

galacturonic, shikimic, quinic, glutamic and aspartic acids.

Boysenberries Citric, malic, and Isocitric acids.

Cherries Malic, citric, tartaric, succinic, quinic, shikimic, glyceric and glycolic

acids.

Crabapple Malic

Cranberries Citric, malic and benzoic acids.

Currants Citric, tartaric, malic and succinic acids.

Elderberries Citric, malic, shikimic and quinic acids.

Figs Citric, malic and acetic acids.

Gooseberries Citric, malic, shikimic and quinic acids.

Grapefruit Citric, tartaric, malic and oxalic acids.

Grapes Malic and tartaric (3:2), citric and oxalic acids.

Kiwifruit Citric

Kumquat Citric

Lemons Citric, malic, tartaric and oxalic acids (no Isocitric acid)

Limes Citric, malic, tartaric and oxalic acids.

Loganberry Malic, citric acids

Nectarine Malic

Orange Peel Malic, citric and oxalic acids.

Orange Citric, malic and oxalic acids.

Passionfruit malic

Peaches Malic and citric acids

Pears Malic, citric, tartaric and oxalic acids

Pineapples Citric and malic acids.

Plums Malic, tartaric and oxalic acids.

Raspberry Citric

Rosehip Malic

Quinces Malic acid (no citric acid)

Salad Citric and malic

Strawberries Citric, malic, shikimic, succinic, glyceric, glycolic and

aspartic acids.

Tangerine Citric

Youngberries Citric, malic and Isocitric acids.

n = 37

85 % contains citric acid !

Where is this acidity coming from ? (1)

Fruits (1)

Beans Citric, malic and small amounts of succinic and fumaric acids

Broccoli Malic and citric (3:2) and oxalic and succinic acids.

Carrots Malic, citric, Isocitric, succinic and fumaric acids.

Mushrooms Lactarimic, cetostearic, fumaric and allantoic acids.

Peas Malic acid.

Potatoes Malic, citric, oxalic, phosphoric and pyroglutamic acids.

Rhubarb Malic, citric and oxalic acids.

Tomatoes Citric, malic, oxalic, succinic, glycolic, tartaric, phosphoric,

hydrochloric, sulphuric, fumaric,

pyrrolidinonecarboxylic and galacturonic acids.

Vegetables (2)

Majority of acidic

vegetables contains

citric acid


Natural occurrence of citric acid in fruits and vegetables

Plant Citric Acid, wt %

Lemons 4.0 - 8.0

Grapefruit 1.2 - 2.1

Tangerines 0.9 - 1.2

Oranges 0.6 - 1.0

Blackcurrant 1.5 - 3.0

Red Currant 0.7 - 1.3

Raspberries 1.0 - 1.3

Strawberries 0.6 - 0.8

Apples 0.008

Potatoes 0.3 - 0.5

Tomatoes 0.25

Asparagus 0.08 - 0.2

Turnips 0.05 - 1.1

Peas 0.05

Corn Kernels 0.02

Lettuce 0.016

Median : 0,57 %

or 5,7 g/L

Soft Drinks, Citric Acid, Impacts find tangy flavour.

Sequesters harmful heavy metal ions

0.25 - 0.4%

Soft Drinks, Sodium Citrate, Offers agreeable,

cooling, saline taste. Assists in retaining

carbonation

0.1%

Wine, Citric Acid, Prevents or dissolves ferric

turbidity caused by Tannin iron or phosphate iron

complexes.

0 - 0.3%

Candies, Citric Acid, Enhances flavour of fruits and

berries. Promotes sucrose inversion.

0.5%

Canned Fruits and Vegetables, Citric Acid, Allows

reduction of retorting temperature. Preserves

flavour, appearance and consistency.

0.1%

Jams and Jellies, Citric Acid/Sodium Citrate, pH

adjustment for optimal pectin gelling

0 - 0.3%

Gelatin Desserts, Citric Acid/Sodium, Citrate pH

adjustment for optimal gelatin setting. Contributes

to tartness and refreshing properties.

2.5%

Processed Cheese, Sodium Citrate, Stabilises

emulsified fat. Complexes calcium ions. Improves

microbiological stability.

3 – 4%

Antioxidants, Citric Acid, Acts as synergist to

antioxidants due to complexation of heavy metal

ions

0.02%

Additives in food products (3)


What choice of typical pH ? (1)

• List of n = 488 type of foods pH < 4,5 : n = 143

Median : pH = 3.45

P95 : pH = 2.69

P99 : pH = 2.00

• pH of simulant B : acetic acid 3 % : pH = 2,5

Citric acid : 1 g/L : pH = 2,7

Citric acid : 5 g/L : pH = 2,35

What choice of typical pH ? (2)

From the point of view of the alloy or metal ?

a. quicker passivation for stainless steel then more realistic if reuse of utensil.

Acetic acid

Citric acid

Malic acid

b. More realistic than acetic acid for aluminium

0

1

2

3

0 50 100 150

Co

ncen

trati

on

s

(mg

/dm

2)

Time (min)

Comparison : releases in lemon juice and citric acid at same pH

Denrée alim Jus de Citron aps minéralisation pH 2,51

0

5

10

0 50 100 150

Co

nc

en

tra

tio

n

(mg

/dm

2)

Time (min)

Release of Al in acetic acid at differents pH

Acide Acétique Ph 3,5

Unrealistic

Real situation :

lemon juice

What about practice in the lab ?

• Purities of citric acid and acetic acid for metal

analysis are comparable

• The price of citric acid is not higher than acetic acid

• Disponibility : ok for the two

• Manipulation of citric acid is easier, particularly for hot

temperatures (Cf. vapour of acetic acid)

The SRL

The guidelines

1. New simulants



Conclusion



2) New concept for repeated use (1) :

Sum First and Second release

• “Where a material or article is intended to come into repeated contact with foodstuffs,

the release test(s) shall be carried out successively three times. Its compliance

shall be checked on the basis of the level of release recorded from the third test.

Of the release of the first and second tests : the sum of the results of the first and second

tests shall not exceed an exposure of one week.

tests shall not exceed an exposure of 7 times SRL.

• JECFA uses the term PTWI, or provisional tolerable weekly intake, for

contaminants that may accumulate in the body. The weekly designation is

used to stress the importance of limiting intake over a period of time for

such substances.

New concept for repeated use (2) :

The SRL

The guidelines

1. New simulants



Conclusion

I. Resolution on Metal and Alloys


3) Problem of measurement of utensils

• Plastics Regulation was essentially designed for

packaging.

Example : concept of 6dm²/kg problems for non

packaging food appliances : typically utensils.

• Procedure necessitates to measure the surface

of the considered utensils :

Therefore practically the result is to measure the

surfaces of objects such as whisk or sieve !!

Exposure is not related to surface of utensil

Relation Surface- typical food wheight in

contact

0

100

200

300

400

500

600

0,00 2,00 4,00 6,00 8,00 10,00

Surface (dm²)

typ

ical fo

od

weig

ht

in c

on

tact

Problem

very big

dispersion !!

Other system is

necessary :

see next

presentation of

Ingo Ebner

The SRL

The guidelines

1. New simulants



Conclusion



Conclusions

1) New better adapted concepts where introduced

by implementation by MS and consultation of

industry representative

2) This standards are already applied by a lot of

labo’s in EU and implemented in controls by

some authorities of members states

3) Some conventionals concepts where replaced

by scientifically or technologically based

concepst

Thank you for your attention!

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