contaminants in oils and fats in terms of food safety...

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

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

Physical Hazards

Chemical Hazards

Biological Hazards

Primary

Safety Hazards

of Edible Oils

and Fats


Mechanical Migration

Foreign Substance

Package Material

Migration

1.1 Physical Hazards


BaP

Pesticide Residues

Plasticizers Trans Fatty

Acids

3-MCPD

1.2 Chemical Hazards


Alfatoxin Zearalenone

1.3 Biological Hazards


2. Processing Sections Bringing in Hazards and Causes

2. Processing Sections Bringing

in Hazards and Causes

Processing Sections

Bringing in Hazards

Oilseed Plantation and

Storage

Processing

Consumer Behaviors

2.1 Oilseed Plantation and Storage

Heavy Metal

Contamination Dioxin Contamination



Oilseed

Deterioration

Pesticide

Residues

2.1 Oilseed Plantation and Storage



2.1.1 Oilseed Plantation and Storage ---Heavy Metal Contamination

2x105 km²

1/6 As Hg Pb Cd



· 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,

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



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

GuangXi SiChuan GuiZhou YunNan >100ppb Southern: AFT Dominated

Northern：Depends on Weather

Regional

Difference

2.1.3 Oilseed Plantation and Storage---Alfatoxin (AFT) Contamination



2.2 Processing

Mechanical

Migration Package

Material

Migration



TFAs 3-

MCPD

2.2 Processing



Plasticizers

BaP

2.2.1 Processing---Plasticizer Migration

Contaminated Products

Edible Oils

Heating



Animal Experiment

of Biology Faculty

in Hong Kong

Baptist University

Ovulation

Reproductive Organs

Endocrine Functions

Fertility

Carcinogenesis/

Teratogenesis

Plasticizers

BaP Highly Toxic

One Type

of PAHs

Quality of Solvent

Temperature Control

Roasting/

Baking

Contact

Material

Migration

2.2.2 Processing---BaP



Mammary Cancer

2.2.3 Processing---Trans fatty acid

Hydrogenation/

Deodorization

Cardiovascular Diseases

Alzheimer's Disease

Type II Diabetes



3-MCPD-di-ester 3-MCPD-mono-ester 3-MCPD-2-mono-ester

(3-monochloropropanediol) 2.2.4 Processing--- 3-MCPD



2.3 Consumer Behaviors --- Rancidity



Aging Effect

Carcinogenesis

Cellular Respiration Blockage

Cardiac-Cerebral Vascular Disease

·R



2.3 Consumer Behaviors --- Rancidity


Detection

Elimination

Prevention

3.1 Preventive Measures

• Oils and Fats Processing

• Oilseeds Planting • Oilseeds Storage • Oils and Fats Processing

• Oilseeds Planting • Oilseeds Storage

• Consumer Behaviors


GAP GMP

HACCP Science

Popularization

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

*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

…………



3.1.1.1 Methods to Lower TFA in Edible Oils and Fats---Formula Modification

Change the Functions and Properties of Triglyceride without Increasing TFA Content by Interesterification to Reconstruct Fatty Acids



3.1.1.2 Methods to Lower TFA in Edible Oils and Fats--- Interesterification

Ordinary

Oils and

Fats

Hydraulic

Pressing

Stearine

Olein

Different

Functions and

Properties to

Meet Different

Needs



3.1.1.3 Methods to Lower TFA in Edible Oils and Fats--- Fractionation

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

%



Refining

Degumming

Deacidification

Decolorization

Deodorization（about 250 ℃)

T (Tray column) > T (Packed column)

Slight impact on TFA content

Greatly increases TFA content



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.



3.1.1.5 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

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



• 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



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



3.1.3.1 Methods to Lower 3-MCPD in Edible Oils and Fats---Degumming





3.1.3.2 Methods to Lower 3-MCPD in Edible Oils and Fats--- Neutralization



Temperature More Important Parameter than Time

3.1.3.3 Methods to Lower 3-MCPD in Edible Oils and Fats--- Deodorization

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



CFSA : China National Center for Food Safety Risk Assessment

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



3.1.4 CFSA-Yihai Kerry Joint Investigative Research of PAHs in Edible Oils

Interesterification

Deodorization

Deacidification Dehydration

Decolorization

Impurity Removal

3.2 Elimination Measures


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


for Edible Oil and Fats---Elimination Measures

Before Adding Decoloring Clay

After Adding Decoloring Clay

Content Change of PAHs in Crude Camellia Oil During Processing



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

-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



• Raw Material : Camellia Oil • BaP Content : 7.3 ppb • Adsorbent : Active Charcoal

• Adsorptive Temp. : 18℃ • Adsorptive Time: 3hr • Stirring Speed : 50rpm

AFT

Rinsing Treatment

Adsorptive

Treatment UV

Irradiation

Ozonation



3.2.2 Methods to Lower AFT in Edible Oils and Fats---Refining

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（%）



3.2.2 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

4. Food Safety Event Review of Edible Oil in China

Waste Oil


---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

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


---Waste Oil

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


---Waste Oil

Detection Management


---Waste Oil

Identification

Precaution

Prevention Elimination

Safety Insurance for Edible Oils and Fats

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.

Thanks for the effort from Ms.Ye

——Thank you ——

contaminants in oils and fats in terms of food safety...

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