PHTHALATE CONTAMINATION IN FOOD PRODUCT

PT. ALS INDONESIA

Melissa Dita Novianti, M.Sc.

AGENDA

• OVERVIEW OF PHTHALATE CHEMISTRY

• MEASUREMENT OF PHTHALATE CONTENT IN FOOD

• REQUIREMENTS

PHTHALATE CHEMISTRY

• 1,2-Benzendicarboxylic acid esters ~Phthalate

• Plasticisers for polymers such as PVC

• Also used in packaging, adhesives, paints, films, cosmetics

• Global consumption of Phthalates ~ 8 million tons (WHO).

• Constant present in all human exposure

pathway. Phthalate

COMMONLY USED PHTAHALATES

DEHP – Di(2-ethylhexyl) phthlate

BBP – Benzyl butyl phthalate

DIDP – Di-isodecyl phthalate

DBP – Dibutyl phthalate

DNOP – Di-n-octyl phthalateDINP – Di-isononyl phthalate

Phthalates Applications

Food packagingMedical devicesFlooring and wall covering FurnitureCables, wires and hosesClothes ToysCar interiorPaints, printing ink and adhesives

PTHALATE CHARACTERISTIC

• Soluble in oil• Insoluble in water• Able to resist high

temperature• Degrade under exposure

to sunlight• Metabolised under

aerobic microbial activity

ENDOCRINE DISRUPTORCHEMICAL

Chemicals that interfere withendocrine (or hormon system) in

animals including humans.

PTHALATES EXPOSURE

• Food (Fatty oily food)

• Air

• Water

• Cosmetics

• Pharmaceutical

PHTHALATES Enter the Body

How do phthalate enter the environment?

• Ambient air: Smoke-stack emission, vaporization from plastic product.

Unlikely exceed 0.1 ug/m3. Reported 1.0 ug/m3 (plastic factory).• Indoor air: Air fresheners, cosmetic product, fabrics, Reported 1-10 ug/m3.

• Surface water: insoluble. <10 ppb, rarely exceed 10 ppm.• Drinking water: stored in polyethylene bottles. USEPA 6 ppb

How do phthalates get into the food?

• Direct contact with phthalate containing of processing equipment

• Packaging material is a major source of phthalates in the diet

• especially in food items of high lipid contents.

• Heating food in the ready-to-eat packages facilitates phthalate migration from packaging material to food.

• Frying in a Teflon coated pan

• Plastic packaging

• Printed ink on wrapping films in confectionary and snack products

• Processing, packaging, and condensation in cream and cheese products.

• Leaching from PVC gloves used during food preparation

How do phthalates get into the food?

PHTHALATE INVESTIGATED

FOOD MATRICES INVESTIGATED

Phthalates Migration from Food Grade PVC film

Amount of migration of DEHP from PVC film into meat was influenced

by temperature, time, fat content and pH value.

Amount of Migration DEHP Increased

Migration DEHP (mg/Kg)

Meat size, temperature, contacting film/meat (hours)

1. Time prolonging and Temperature increasing

1961.92 ~ 2000 75.12 mg/dm2, 90oC, film/meat contacting 0.5h

2. Fat content adding 2255.91 (45.2%) 55.68 mg/dm2, 20oC, film/meat contacting 60 h

3. The highest pH6

1281.59 ~ 1300 49.00 mg/dm2, 20oC, film/meat contacting 48 h

Phthalates Migration from Food Grade PVC film

Ultraviolet radiation and microwave could enhance the migration of DEHP from PVC film into meat

Amount of Migration DEHP Increased

Migration DEHP (mg/Kg)

Meat size, temperature, contacting film/meat (hours)

1. Ultraviolet radiating 39.55% higher than control samples

12h

2. Microwave heating 534.92Control sample ND

13.76 mg/dm2, 16s, 850W

Phthalates Migration from Food Grade PVC film

The amount of DEHP in contaminated samples significantly decreased after cooking and frying

Amount of Migration DEHP Increased

Migration DEHP (mg/Kg)

Meat size, temperature, contacting film/meat (hours)

1. After cooking Lower 50.96%From 536.80 to 263.26

30 min

2. After frying Lower 61.49%From 536.80 to 206.70

3 min

* Amount of migration of DEHP differed in different foods

• DEHP added as a clouding agent into sports and soft-drinks in Taiwan.

TAIWAN SCANDAL

Clouding Agent

Production

Manufacture

• Juicy drink

• Yoghurt

• Jam

• Sports drink

• Jelly

• Fruit cocktail

USES OF CLOUDING AGENT

DEHP Contamination in Food

• Minuman Impor Taiwan Tercemar DEHP

Taiwan dan Filipina memperingatkan bahwa sejumlah minuman olahraga kemungkinan terkontaminasi bahan kimia DEHP yang bisa menyebabkan infertilitas dan menghambat pertumbuhan organ seksual pria.

MANILA, Philippines -

Some Taiwanese food and drinks contaminated with Di (2-ethylhexyl) phthalate (DEHP), a product used in making plastic, have reached the Philippines. ABS-CBN News.com

KUALA LUMPUR, June 3 Yahoomalaysia news

. They are Cranberry Juice Cocktail and Cranberry Refreshers with the Ocean Spray brand, Mango Flavour Coconut Jelly and Fruitgurt Yogurt .

Snacks and drinks from Taiwan tainted withDEHP and di-isononyl phthalate (DINP) are banned in Malaysia.

DEHP Contamination

Scare

MEASUREMENT TECHNIQUES

• Sample preparation / clean up

• Instrumentation

• Method performance

• Quality Assurance

Food Matrices

FOOD TESTING

SAMPLE STORAGE

Source Contamination

• Sampling container

• Aluminium

• Plastic packaging

• Glassware

• Original food packaging should be used for sample storage

• Samples phthalate analysis are stored cooled.

Sample Clean Up

• Liquid/liquid partitioning

• Solid Phase Extraction

• Gel permeation chromatography

Objectives of Sample Clean Up

INSTRUMENTATION

• GC MS

• GC FID

• GC ECD

• HPLC DAD

• HPLC MS/MS

Gas Chromatography Mass Spectrometry

CHROMATOGRAM – Scan mode :20ppm

Dimethylphthalate – SIM mode

Diethylphthalate – SIM mode

Di-butyl phthalate– SIM mode

Benzyl butyl phthalate – Scan mode

Bis-2-ethylhexyl phthalate – SIM mode

Di-n-octyl phthalate– SIM mode

Summary of phthalates analyzed

Phthalates type Abb. Retention Time (min)

SIM ions detail

Dimethylphthalate DMP 7.474 163.05, 77.05, 50.05

Diethylphthalate DEP 8.171 149.00, 150.00, 65.00, 75.95

Di-n-butylphthalate DIBP 9.796 149.00, 150.00, 205.05

Benzyl butyl phthalate BBP 11.293 149.00, 91.05, 206.05

Bis-2-ethylhexyl phthalate

DEHP 11.858 148.95, 167.00, 57.05, 71.05

Di-n-octyl phthalate DNOP 12.475 149.00, 279.90, 150.70

QA/QC

• BLANK VALUES Hardly constant, need to be well controlled

• “ A reading originating from the matrix/reagent in the measurement device, which contributes to the result in the analytical procedure”

• Start running

• End running

• Each food sample

• All apparatus used were GLASS• Blank : High purity Hexane is free from

phthalates.

FALSE POSITIVE

• Quality control charts• Replicate sample• Avoiding the use of plastic material during sample

preparation• Checking chemicals before use, • Distillation • Heating of glassware in a furnace 2h; 400oC; • Store it until use in desiccators • Rinsing glass ware with solvents • Exchanging frequently wash solvents • Performing runs without injection to clean the instrument

QA/QC

Method Performance

• Limit of Reporting

GCMS scan mode : 1 ppm

GCMS SIM mode : 0.5 ppm LCMS/MS : 0.05 ppm

• Recovery : Spiking 80-110%

• USEPA Drinking water Maximum Contaminant Level 6 ppb for DEHP

• Ministry of Health, Malaysia : 1 ppm for food products

• The Tolerable Daily Intake (TDI) of DEHP, as established by the European Union, is 0.05mg/kg body weight/day and has incorporated a safety margin of 100 times.

REQUIREMENTS : OVERVIEW

Thank You