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.
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?
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
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
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
INSTRUMENTATION
• GC MS
• GC FID
• GC ECD
• HPLC DAD
• HPLC MS/MS
Gas Chromatography Mass Spectrometry
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
• 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