Food Contact Materials: Migration testing using MS - Waters Corporation Food Safety

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Food Contact Materials: Migration testing


Food manufacturing equipment

– Belts, gaskets, lubricants, etc.

Food packaging

– Paper, plastic, cartonboard, glass, etc.

Food preparation wares

– Crockery and utensils (e.g. chopping boards, whisks)

– Gloves, apron, etc.

Dining wares

– Cutlery

– Bowl, plate, etc.

Food Contact Materials/ Substances


Migration involves the mass transfer from an external source into

food by sub microscopic processes impacting food safety and quality

Migration can occur by

1. Diffusion

– Classified as direct contact migration as it’s physicochemical dependant

– Packaging components penetrate and diffuse across packaging material

layers due to chemical interactions

2. Gas phase

– Indirect contact migration where molecules travel through gas phase

– Volatile components can migrate or “jump” from material into foods

3. Set off

– Migration due to set off of components during manufacture or storage

Migration


Isopropylthioxanthone (ITX)

– 2005: Ink curing agent detected in cardboard packaged milk

Epoxydised soy bean oil (ESBO)

– 2005: Swiss survey of jarred foods identified concentrations exceeding the TDI allowance

Diethylhexyl phthalate (DEHP)

– 2011: Clouding agent in probiotics substituted by probable carcinogenic compound in order to cut costs

Primary aromatic amines (PAAs)

– 2007: Poorly manufactured polyamide utensils leach carcinogenic amines

Bisphenol A (BPA)

– Recent concern involving infant feeding bottles

International Migration Alerts


International Regulations

European Union

– Framework: 1935/2004/EC

United States

– Code of Federal Regulation Chapter 21

– Component specific approach

Japan

– Framework based on Food Sanitation Act, 1947

China

– Food Safety Law, 2009

South America

– MERCOSUR Resolution GMC 3/92

Australasia (New Zealand and Australia)

– Limited regulations in place; refer to EU and FDA for regulatory guidance


Migration modelling software

– Diffusion theory and partitioning effects

– Free and commercial softwares available

– Models provide overestimation of migration

Migration into food simulants

– Mimic food types

– Foreseeable worst case scenario

– Minimise matrix effects

Migration into foods

– Migration under real conditions

– Various sample cleanup required

Migration Testing


Complex formulation of materials

– Food packaging: monolayer/ multilayer

– Use of recycled materials

Consider food type to be packaged in final product or intended

purpose

Set- off migration

– Incomplete curing resulting in transfer into foods

– ITX case

Non intentionally added substances

– Impurities within raw materials

– Polymer, additive degradation or reaction products

– Contaminants

Challenges associated with FCMs


“Materials and articles, including active and intelligent materials and

articles, shall be manufactured in compliance with good

manufacturing practice so that, under normal or foreseeable

conditions of use, they do not transfer their constituents to food in

quantities which could:

(a) endanger human health;

(b) bring about an unacceptable change in the composition of the food;

(c) bring about a deterioration in the organoleptic characteristics thereof.”

Directive 1935/2004/EC

All materials and articles intended to come in contact with food

should be manufactured in accordance with good practices

Foundation of FCM legislation


Amount of a specified component that migrates from the food contact

material or article to the food during contact permitted by regulations:

Specific Migration Limit (SML)

Regulations and testing ensures safety limit based on toxicological

data and risk of exposure

Regulated limits set on permitted migrates

– For example Pb from ceramics; BADGE from can coatings

– Positive list associated in EU (for plastics) and China

Specific Migration


Challenges associated with non- targeted analysis

– Optimisation of sample prep, analytical instrumentation, ionisation mode,

etc. is a compromise

Requires prior knowledge of formulation of food contact materials

Method workflow under development among research groups

– Nerin, et al. DOI: 10.1016/j.aca.2013.02.028

– Koster, et al. DOI: 10.1080/19440049.2013.866718

– Cabovska, Waters application note 720005326en

Non intentionally added substances


XEVO Universal source: Compatibility Options


Known to migrate from poorly manufactured polyamide kitchen utensils

(black)

Carcinogenic compounds

EU SML (T): not detectable i.e. < 0.01 mg.kg-1 of food or food simulant

– Sum of PAAs; no definitive list, however specific compounds included in Annex

I of 10/2011/EU

Repeat article tested at worse case scenario for foreseeable use

– e.g. spoon: in simulant B (3 % aq. acetic acid) at 100 °C for 2 hrs x 3

Primary aromatic amines (PAAs)


Push button

Quick start up

Pre optimised conditions

AcQuity QDa Detector: An accessible mass detector


PAAs in dyes by AcQuity QDa

Increased Sensitivity Selectivity

Decreased

Sample preparation


Phthalates in distilled spirits

Phthalates cover a large group of compounds, esters of phthalic acid Known toxic effects

− Considered endocrine disruptors, related to reproduction in animal studies Migration can occur during production and storage, from packaging materials,

coatings, equipment coatings, sealants, etc.


Challenges in phthalate analysis

Background ~7e4

DBP at 100 ppb

Traditionally, analysed by gas chromatography

– Derivatisation and/ or extraction required

– Non selective m/z 149 monitored for multiple compounds

Growing interest liquid chromatography method

– Reduced sample preparation: dilute and shoot

– Improved selectivity on m/z transitions

Ubiquitous contaminants

– Significant background impacts accurate

quantification


Isolator column: Overview

Ubiquitous contaminants

AcQuity C18 isolator column

− Part number: 186004476

Isolator separates background

contaminants from analytes of

interest

Isolator column

Sample injector

Solvent mixer


Isolator column: Contaminant separation

BBP Background BBP contaminant


Sample Analysis

+

Dilute 1:1 with water and place in vial for LC-MS/MS analysis

Sample Name Spirit type

1. Sample A Brandy (brand A)

2. Sample B Gin

3. Sample C Whiskey (brand

A)

4. Sample D Brandy (brand B)

5. Sample E Tequila

6. Sample F Whiskey (brand

B)


Sample F spiked at 100 µg.l-1

DINP

DNOP

DEHP

BBP

DBP

DEP

DMP


Compound name: DMPCorrelation coefficient: r = 0.997256, r^2 = 0.994520Calibration curve: 2819.84 * x + 19543.6Response type: External Std, AreaCurve type: Linear, Origin: Exclude, Weighting: 1/x, Axis trans: None

ppb-0 10 20 30 40 50 60 70 80 90 100

Re

sp

on

se

-0

100000

200000

300000

Compound name: BBPCorrelation coefficient: r = 0.997755, r^2 = 0.995515Calibration curve: 839.103 * x + 1264.79Response type: External Std, AreaCurve type: Linear, Origin: Exclude, Weighting: 1/x, Axis trans: None

ppb-0 10 20 30 40 50 60 70 80 90 100

Re

sp

on

se

-0

20000

40000

60000

80000

Matrix matched calibration curve

BBP R2: 0.996

DMP R2: 0.995

Compound name: DNOPCorrelation coefficient: r = 0.998477, r^2 = 0.996957Calibration curve: 763.204 * x + 168.408Response type: External Std, AreaCurve type: Linear, Origin: Exclude, Weighting: 1/x, Axis trans: None

ppb-0 10 20 30 40 50 60 70 80 90 100

Re

sp

on

se

-0

20000

40000

60000

DNOP R2: 0.997

Phthalate LOD

(S/N > 3) LOQ

(S/N > 10)

DMP < 1 ppb < 1 ppb

DEP < 1 ppb < 1 ppb

DBP < 1 ppb < 1 ppb

BBP < 1 ppb < 1 ppb

DEHP < 1 ppb < 1 ppb

DNOP < 1 ppb < 1 ppb

DINP 5 ppb < 10 ppb


System Specificity: Matrix Blanks

Blank

Spiked at 100 µg.l-1

Blank Blank

Sample A Sample C Sample E

Spiked at 100 µg.l-1 Spiked at 100 µg.l-1


System robustness: 100 replicate injections

Name RSD % Relative Precision

(CV)

DMP 4.55 0.05

DEP 1.87 0.02

DBP 2.05 0.02

BBP 1.95 0.02

DEHP 3.82 0.04

DNOP 5.90 0.06

DINP 4.98 0.05


Restricted use of BPA in

– Polycarbonate infant bottles

– Epoxy resin for sealing packaging

BPA and family are suspected

estrogenic activity and endocrine

disruptor

Bisphenols from resins


The advantage of RADAR Full scan and MRM in one analysis

1. Protein precipitation 2. SPE – OASIS HLB

1. Protein precipitation

2. DisQUE (QuEChERS) 3. SPE – OASIS HLB


Spiked Compounds 1 pg/μL in Samples

S/N > 3


NIAS in adhesives

Non targeted analysis of migrants from adhesives

Headspace GC coupled with single quadrupole MS

APGC coupled with QToF


Atmospheric Pressure Gas Chromatography


Source and Ion Chamber


Charge Transfer

Dry Source

M+. produced

Plasma

Corona Pin

Sample Cone

Make-up gas (N2)


Proton Transfer

Wet Source

M+H+ produced

Plasma

Corona Pin

Sample Cone

Make-up gas (N2)


Xevo Tof MSE

Acquisition of the complete MS Dataset

Low energy

Simultaneous acquisition

Elevated energy

CE ramp applied


Identification of Unknowns

Reproduced with thanks to Prof. Christina Nerin & group, University of Zaragoza

5-chloro-2-methyl-1,2-thiazol-3(2H)-one


APGC-ToF vs HS-GC-EI-Q

Reproduced with thanks to Prof. Christina Nerin & group, University of Zaragoza


Conclusions

Vast and varied area of analysis with international interest increasing

Extensive legislation in place

– Providing solid base for safety and analytical approach

– Exporting to different countries/ states

Analytical challenges faced by food industry

– Important to maintain good communication between suppliers for efficient proof of compliance

Accessible and robust applications available for routine analysis of FCMs

– Specific migration and non-targeted (or NIAS) workflow

Improves consumer confidence and ensures compliance for export with high throughput


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Date post:	16-Apr-2017
Category:	Food
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