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标题(Title)
2014.11.19
Contaminants in Oils and Fats in Terms of Food Safety
---An Updated Concern in China
Ruiyuan Wang Chinese Cereals and Oils Association
Xuebing Xu Wilmar (International) Biotechnology Research & Development Center
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1. Hazards of Edible Oils and Fats
2. Processing Sections Bringing in Hazards and Causes
3. Hazard Control Measures for Edible Oil and Fats
4.Food Safety Event Review of Edible Oil in China
---Waste Oil
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1. Hazards of Edible Oils and Fats
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Physical Hazards
Chemical Hazards
Biological Hazards
Primary
Safety Hazards
of Edible Oils
and Fats
1. Hazards of Edible Oils and Fats
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Mechanical Migration
Foreign Substance
Package Material
Migration
1.1 Physical Hazards
1. Hazards of Edible Oils and Fats
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BaP
Pesticide Residues
Plasticizers Trans Fatty
Acids
3-MCPD
1.2 Chemical Hazards
1. Hazards of Edible Oils and Fats
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Alfatoxin Zearalenone
1.3 Biological Hazards
1. Hazards of Edible Oils and Fats
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2. Processing Sections Bringing in Hazards and Causes
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2. Processing Sections Bringing
in Hazards and Causes
Processing Sections
Bringing in Hazards
Oilseed Plantation and
Storage
Processing
Consumer Behaviors
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2.1 Oilseed Plantation and Storage
Heavy Metal
Contamination Dioxin Contamination
2. Processing Sections Bringing
in Hazards and Causes
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Oilseed
Deterioration
Pesticide
Residues
2.1 Oilseed Plantation and Storage
2. Processing Sections Bringing
in Hazards and Causes
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2.1.1 Oilseed Plantation and Storage ---Heavy Metal Contamination
2x105 km²
1/6 As Hg Pb Cd
2. Processing Sections Bringing
in Hazards and Causes
· Cd Contamination:
HuNan Province
HuBei Province
Guangxi Province
· Pb Poisoning:
GanSu Province, JiangSu Province,
ShanXi Province, YunNan Province,
HuNan Province, FuJian Province,
GuangDong Province,
ZheJiang Province,
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Highly
Toxic Cl
7-11
years
Lymphatic
System Blood System
Reproductive
System
800℃
21s
Long-term
Accumulation
2.1.2 Oilseed Plantation and Storage---Dioxin Contamination
2. Processing Sections Bringing
in Hazards and Causes
Uncontrolled
Burning
Transportation Waste Disposal
Others
Waste
Burning
Metal
Production
Electricity Production
and Heat Supply
Mineral Industry
Production and Handling
of Chemicals
Dioxin Emission Distribution
in Different Industries
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GuangXi SiChuan GuiZhou YunNan >100ppb Southern: AFT Dominated
Northern:Depends on Weather
Regional
Difference
2.1.3 Oilseed Plantation and Storage---Alfatoxin (AFT) Contamination
2. Processing Sections Bringing
in Hazards and Causes
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2.2 Processing
Mechanical
Migration Package
Material
Migration
2. Processing Sections Bringing
in Hazards and Causes
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TFAs 3-
MCPD
2.2 Processing
2. Processing Sections Bringing
in Hazards and Causes
Plasticizers
BaP
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2.2.1 Processing---Plasticizer Migration
Contaminated Products
Edible Oils
Heating
2. Processing Sections Bringing
in Hazards and Causes
Animal Experiment
of Biology Faculty
in Hong Kong
Baptist University
Ovulation
Reproductive Organs
Endocrine Functions
Fertility
Carcinogenesis/
Teratogenesis
Plasticizers
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BaP Highly Toxic
One Type
of PAHs
Quality of Solvent
Temperature Control
Roasting/
Baking
Contact
Material
Migration
2.2.2 Processing---BaP
2. Processing Sections Bringing
in Hazards and Causes
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Mammary Cancer
2.2.3 Processing---Trans fatty acid
Hydrogenation/
Deodorization
Cardiovascular Diseases
Alzheimer's Disease
Type II Diabetes
2. Processing Sections Bringing
in Hazards and Causes
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3-MCPD-di-ester 3-MCPD-mono-ester 3-MCPD-2-mono-ester
(3-monochloropropanediol) 2.2.4 Processing--- 3-MCPD
2. Processing Sections Bringing
in Hazards and Causes
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2.3 Consumer Behaviors --- Rancidity
2. Processing Sections Bringing
in Hazards and Causes
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Aging Effect
Carcinogenesis
Cellular Respiration Blockage
Cardiac-Cerebral Vascular Disease
·R
2. Processing Sections Bringing
in Hazards and Causes
2.3 Consumer Behaviors --- Rancidity
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3. Hazard Control Measures for Edible Oil and Fats
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3. Hazard Control Measures for Edible Oil and Fats
Detection
Elimination
Prevention
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3.1 Preventive Measures
• Oils and Fats Processing
• Oilseeds Planting • Oilseeds Storage • Oils and Fats Processing
• Oilseeds Planting • Oilseeds Storage
• Consumer Behaviors
3. Hazard Control Measures for Edible Oil and Fats
GAP GMP
HACCP Science
Popularization
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Formula
Modification
Interesterification
Fractionation
Hydrogenation
Process
Improvement
Replace Hydrogenated Oils or Fats with Special Fatty
Acid Composition Products (Such as Palm Oil or Oils
That Are High in Oleic Acid/ Low in Linolenic Acid) to
Reduce TFA .
Interesterification Under the Presence of Enzymes or
Chemical Catalyst Is An Ideal Technique for Producing
Low TFA Products.
To Obtain Products With Different Properties by
Fractionation without TFA formation.
Use Pt or Pd to Substitute Ni as Catalyst to Lower
Hydrogenation Temperature, which results in TFA
Reduction.
3. Hazard Control Measures
for Edible Oil and Fats---Preventive Measures
3.1.1 Methods to Lower TFA in Edible Oils and Fats
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*Oil A,B,C,D Are Free of TFA
Oil A
Oil B
Oil C
Oil D
Oils Not Containing TFA
Oils Containing TFA Decreasing the Usage
Increasing the Usage Modification
…………
3. Hazard Control Measures
for Edible Oil and Fats---Preventive Measures
3.1.1.1 Methods to Lower TFA in Edible Oils and Fats---Formula Modification
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Change the Functions and Properties of Triglyceride without Increasing TFA Content by Interesterification to Reconstruct Fatty Acids
3. Hazard Control Measures
for Edible Oil and Fats---Preventive Measures
3.1.1.2 Methods to Lower TFA in Edible Oils and Fats--- Interesterification
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Ordinary
Oils and
Fats
Hydraulic
Pressing
Stearine
Olein
Different
Functions and
Properties to
Meet Different
Needs
3. Hazard Control Measures
for Edible Oil and Fats---Preventive Measures
3.1.1.3 Methods to Lower TFA in Edible Oils and Fats--- Fractionation
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TFA
%
0
0.5
1
1.5
2
2.5
3
cold pressing hot pressing Chemical Refining
Impacts of Different Processing Technologies on TFA content
(Sunflower Seed Oil)
Cold Pressing
Hot Pressing
Chemical Refining
3.1.1.4 Methods to Lower TFA in Edible Oils and Fats---Processing Technology
TFA
%
3. Hazard Control Measures
for Edible Oil and Fats---Preventive Measures
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Refining
Degumming
Deacidification
Decolorization
Deodorization(about 250 ℃)
T (Tray column) > T (Packed column)
Slight impact on TFA content
Greatly increases TFA content
3. Hazard Control Measures
for Edible Oil and Fats---Preventive Measures
3.1.1.5 Methods to Lower TFA in Edible Oils and Fats---Refining
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250248246244242240238236
脱臭温度
2.500
2.250
2.000
1.750
1.500
1.250
反
式
酸
含
量
R S q Line a r = 0.991
Take Soybean Oil As An Example, TFA Content Is Positively Correlated With
Deodorization Temperature When Other Conditions Remain The Same.
3. Hazard Control Measures
for Edible Oil and Fats---Preventive Measures
3.1.1.5 Methods to Lower TFA in Edible Oils and Fats---Refining (Deodorization)
R - correlation coefficient
R=0.996
P<0.01
Temp.
TFA
Co
nte
nt
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Name of Plasticizers in Chinese Abbr. Name of Plasticizers in Chinese Abbr.
邻苯二甲酸二甲酯 DMP 邻苯二甲酸丁基苄基酯 BBP
邻苯二甲酸二乙酯 DEP 邻苯二甲酸二(2-丁氧基)乙酯 DBEP
邻苯二甲酸二异丁酯 DIBP 邻苯二甲酸二环己酯 DCHP
邻苯二甲酸二丁酯 DBP 邻苯二甲酸(2-乙基)己酯 DEHP
邻苯二甲酸二(2-甲氧基)乙酯 DMEP 邻苯二甲酸二苯酯 -
邻苯二甲酸二(4-甲基-2-戊基)酯 BMPP 邻苯二甲酸二正辛酯 DNOP
邻苯二甲酸二(2-乙氧基)乙酯 DEEP 邻苯二甲酸二壬酯 DNP
邻苯二甲酸二戊酯 DPP 邻苯二甲酸二异壬酯 DINP
邻苯二甲酸二己酯 DHXP
3.1.2 Plasticizers detectability of R&D Center, Wilmar
Detection Limit:DMP,DEP,DIBP,DBP,DMEP,DEEP,DEHP: 0.25mg/kg
BMPP,DPP,DHXP,BBP,DBEP,DCHP,DNOP,DNP,DINP: 1.0mg/kg
Chinese National Standard GB/T 21911-2008 1.5mg/kg
3. Hazard Control Measures
for Edible Oil and Fats---Preventive Measures
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• No Need to Add Plasticizers in Oil Products
• Control Environmental Migration
• Strictly Follow Provision No. 551
Raw Materials and Additives
• Metal Gaskets for Pipeline Joints
• GMP
Production Processes
• Requirements for Package Materials Not Containing Plasticizers From Suppliers
• Suppliers Audit and Material Inspection
Package Material
3.1.2 Control Measures for Plasticizers
3. Hazard Control Measures
for Edible Oil and Fats---Preventive Measures
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Inspection of Each Suppliers
Workshops
3.1.2 Risk Assessment of Package Material for Edible Oils
in R&D center, Yihai Kerry Group, 2007
Concern Raised
Inspection of PET Bottle and
Bottle Cap
DEHP
GB/T 21911-2008
GB/T 21928-2008
Raw Materials/ Additives
Suppliers Screening
Sustained Attention
3. Hazard Control Measures
for Edible Oil and Fats---Preventive Measures
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3.1.3.1 Methods to Lower 3-MCPD in Edible Oils and Fats---Degumming
3. Hazard Control Measures
for Edible Oil and Fats---Preventive Measures
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3. Hazard Control Measures
for Edible Oil and Fats---Preventive Measures
3.1.3.2 Methods to Lower 3-MCPD in Edible Oils and Fats--- Neutralization
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3. Hazard Control Measures
for Edible Oil and Fats---Preventive Measures
Temperature More Important Parameter than Time
3.1.3.3 Methods to Lower 3-MCPD in Edible Oils and Fats--- Deodorization
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PAHs
• Important organic contaminants
•Toxicity:carcinogenicity teratogenicity mutagenicity
Exposure
•Food(Edible oils)
•Environment migration
•Food processing
Assessment
• JECFA, FAO/WHO, 2005
• SCF, 2002
•WHO/IPCS, 1998
Limitation
•GB 2762-2012 (μg/kg): BaP≤10 in oils
•835/2011 (EC) (μg/kg) : BaP≤2, PAH4≤10 in oils
Objectives
•PAHs content in different oils
• Identify highly contaminated oil varieties
•Confirm key process sections of PAHs contamination
• Lower PAHs exposure
3.1.4 CFSA-Yihai Kerry Joint Investigative Research of PAHs in Edible Oils
3. Hazard Control Measures
for Edible Oil and Fats---Preventive Measures
CFSA : China National Center for Food Safety Risk Assessment
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PAHs detection in two different labs
Risk assessment of PAHs in edible oils
Strengthen risk management to lower
PAH exposure
Dietary exposure investigation of
edible oils
Take measures to
reduce PAHs contamination
Identify highly contaminated oil
varieties, processes
EU15+1 PAHs
(7×5×3=105 ) (Oils × Processes× Brands)
Detection method establishment &
comparison
106 Edible oil samples in the
market
DACC-HPLC-FLD & GC-MS/MS Data analysis
3. Hazard Control Measures
for Edible Oil and Fats---Preventive Measures
3.1.4 CFSA-Yihai Kerry Joint Investigative Research of PAHs in Edible Oils
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Interesterification
Deodorization
Deacidification Dehydration
Decolorization
Impurity Removal
3.2 Elimination Measures
3. Hazard Control Measures for Edible Oil and Fats
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3.2.1.1 Methods to Lower PAHs in Edible Oils and Fats
--- Decolorization and Deodorization
Content Change of PAHs in Pressed Peanut Oil Before and After Adding Decoloring Clay
3. Hazard Control Measures
for Edible Oil and Fats---Elimination Measures
Before Adding Decoloring Clay
After Adding Decoloring Clay
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Content Change of PAHs in Crude Camellia Oil During Processing
3. Hazard Control Measures
for Edible Oil and Fats---Elimination Measures
3.2.1.1 Methods to Lower PAHs in Edible Oils and Fats
--- Decolorization and Deodorization
Rat
e o
f R
emo
val /
%
Degummed Oil
Crude Oil
Deacidified Oil
Deodorized Oil
Bleached Oil
Light PAHs
Heavy PAHs
PAHs Equivalent (USEPA)
PAHs Equivalent (Nisbet)
PAHs and Chrysene
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-1
0
1
2
3
4
5
6
7
8
9
0 0.2 0.3 0.4 0.5
BaP
Co
nte
nt ( p
pb)
Active(%)
3.2.1.2 Methods to Lower BaP in Edible Oils and Fats--- Adsorptive Treatment
3. Hazard Control Measures
for Edible Oil and Fats---Elimination Measures
• Raw Material : Camellia Oil • BaP Content : 7.3 ppb • Adsorbent : Active Charcoal
• Adsorptive Temp. : 18℃ • Adsorptive Time: 3hr • Stirring Speed : 50rpm
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AFT
Rinsing Treatment
Adsorptive
Treatment UV
Irradiation
Ozonation
3. Hazard Control Measures
for Edible Oil and Fats---Elimination Measures
3.2.2 Methods to Lower AFT in Edible Oils and Fats---Refining
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0
2
4
6
8
10
12
14
0 0.05 0.1 0.15 0.2 0.25 0.3
AF
T C
on
ten
t (p
pb)
Adsorbent(%)
3. Hazard Control Measures
for Edible Oil and Fats---Elimination Measures
3.2.2 Methods to Lower AFT in Edible Oils and Fats
---Refining (Adsorptive Treatment )
• Raw Material : Peanut Oil • AFT content : 10.8 ppb • Adsorbent : Montmorillonoid
• Adsorptive Temp. : 18℃ • Adsorptive Time: 6hr • Stirring Speed : 30rpm
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4. Food Safety Event Review of Edible Oil in China
Waste Oil
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4.Food Safety Event Review of Edible Oil in China
---Waste Oil
Waste
Oils
1) Processed or Refined Oils From Swill-Cooked Oil
2) Processed or Refined Oils From Pork or Pigskin with Poor Quality
3) Repeatedly Used Oils and Fats
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2014 Taiwan
Chang Guann Co.
• Purchased Large Quantities of Waste Oil →Produced Lard of Poor Quality →Sold to Downstream Enterprises for Food Production
235 Companies
Involved
• Over 510,000 Barrels Produced
• Over 48,000 Barrels Sold
Severe Punishment
• Economic Impact of 160 Million USD
• Fined 1.6 Million USD
4.Food Safety Event Review of Edible Oil in China
---Waste Oil
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Obstacles on Detection of Waste Oil
Unusual Detection Object
· No Fixed Composition
· No Typical Sample
No Characteristic Index
· Characteristic Index
of Regular Edible Oils
Are Not Applicable
for Detection
Lack of Detection Method
· No Standard for
Detection Methods
· Current Monitoring
Scheme Lack of
Specificity
4.Food Safety Event Review of Edible Oil in China
---Waste Oil
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Detection Management
4.Food Safety Event Review of Edible Oil in China
---Waste Oil
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Identification
Precaution
Prevention Elimination
Safety Insurance for Edible Oils and Fats
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Summary
There are increasing safety concerns for oils and fats industry and hazards may come from agriculture production, material handling, processing and management.
Not only does technology matter but also management. Fats and oils industry in China has established systematic safety needs and put them into practice.
China has paid attention to perspectiveness not only on technology but also on practice when facing oncoming food safety issues nowadays.
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Thanks for the effort from Ms.Ye
——Thank you ——