Professional Documents
Culture Documents
5 - Ben Bowen - Final
5 - Ben Bowen - Final
Peroxide Values
2019 Atlanta Customer Symposium | Ben Bowen
KEMIN IS ASSURANCE
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17 years at Kemin. CLS
continually over 14 years.
Also involved with R&D,
Quality, New Business
Development and Tech
Service
9 Years at National By-
Products (now part of
Darling) running their
central laboratory
Ben Bowen 4 years at the USDA Ag
Global CLS Director Research Center
Kemin Nutrisurance researching herbicide
Des Moines, IA USA degradation through the
cell: (515)-490-0405 ground/soil profile
Email: Ben.Bowen@kemin.com 26 years of running lipid
oxidation tests such as
the Peroxide Value test.
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26 Years of Lipid Oxidation Analysis
15,000 = number of PV test’s I’ve personally performed.
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Key Discussion Points in Presentation
1. Why issues exist with PV measurement
2. History of PV Measurement
3. Methods Available
4. Petfood Alliance PV Study
5. PV Measurement Recommendations
6. Future of Lipid Oxidation Measurement
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PEROXIDE
VALUE
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“If there is something in this world that is
difficult to understand, it is income tax.”
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“If there is something in this world that is
difficult to understand, it is income tax.”
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Lipid Oxidation In One Slide
Nonvolatiles
Volatiles
Antioxidant
Unsaturated Lipids
Lubuza, T. P. Kinetics of Lipid Oxidation in Foods, CRC Crit. Rev. Food Technol. 1971. 2, 355-405. www.kemin.com/assurance
© Kemin Industries, Inc. and its group of companies 2019. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
Lipid Oxidation Methods – Dr Frankel
Assessment
Test Sensitivity Precision Information Decision Importance
Sensory High Low High Low
Volatiles (GC) High High High Low
Conjugated Dienes High High Low Low
Carbonyls Low High Low Low
Anisidine Value Low High Low Low
Peroxide Value Low Low Low High
Oxygen Bomb Low High Low Low
TBARS Low High Low Low
Rancimat/OSI Low High Low High
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Lipid and Hydroperoxide History
1770’s – Oxygen was discovered by multiple people.
1815 - Braconnot reported that acids were formed in fats.
1832 - Saussure found that oxygen was absorbed during storage of plant oils.
1780’s-1939 – Continual debate on acids and relationship with rancidity.
1898 – Wijs Iodine Method method developed for measuring double bonds
1909 – Tsujimoto found that oxidation of triglycerides, rather than free fatty acids,
caused rancid flavors.
1920’s-30’s – Many failed attempts to develop rancidity methods.
1925 – Stamm Develop a carbonyl test.
1931 – Lea developed the earliest PV method.
1932 – Wheeler developed a simplified method that was endorsed by the AOCS.
1943 - Conjugated Dienes - spectrophotometer
1950’s – Ferric Thiocyanate - spectrophotometer
1992 – Wolff published FOX II Method (Gupta 1973) - spectrophotometer
1990’s – Dr. Gordon started selling commercial PV Kit (Peroxysafe)
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PV Chemistry – Titration vs Spec.
Classical PV method (titration method)
L• + O2 + •H LOOH
2KI + 2CH3COOH 2HI + 2CH3COO-K+
LOOH + 2HI LOH + H2O + I2
I2 + 2Na2S2O3 2NaI + Na2S4O6
Ferric Thiocyanate method (spectrophotometer)
LOOH + Fe2+ LOH + Fe3+
Fe3+ + SCN- Fe(SCN)2+
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Key Points from PV History
• D.H. Wheeler and C.H. Lea and other’s have debated PV
methods for 80 years.
• Changes to the sample size and the reaction time are the
primary drivers for the PV result, but any variation in the test
procedure may produce erratic results.
3.5
3.2 3.3
Rep 1 Rep 2 Rep 3 3.2
3.0 2.9
2.8 2.8
2.5 2.4
Peroxide Value (meq/kg fat)
2.3 2.3
1.0
0.5
0.0
1 minute 3 minutes 5 minutes 10 minutes 15 minutes
Potassium Iodide Reaction Time
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PV Method Scope
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P-Anisidine Value Scope
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TBARS Scope
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Problem #3 – Hydroperoxides are unstable
PV’s can easily be generated or destroyed. Any method
variation can change the PV result.
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PV Reaction Pathways – Idealized
LH
L●
LOO●
Schaich, K.M. Challenges in Elucidating Lipid Oxidation Mechanisms, AOCS. Press 2013. pg. 6 www.kemin.com/assurance
© Kemin Industries, Inc. and its group of companies 2019. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
Lipid Oxidation Pathways - Actual
LH
E, 1 e– oxidation
Polymers Dimers
Isomerization L• β -Scission
Cis → trans of O2
Uses traditional radical O2
Dimers• Addit
ion Epidioxides•,
chain as a base (in red) Endoperoxides•
-CH=CH- O2 LOO• Cyclization
addition r
fe O2
ns
More fully accounts for : Epoxides• tra Hydrogen
O2
r on
• chemistry leading to many + LO• ct abstraction
le
from LH or
-E
kinds of products + / RH
Epoxides•
LOO+ or LOO–
• many products appearing LOOH
H+
parallel to LOOH
n
atio
hν ∆ Mn+
liz
Scission
yc
C
HO• + •OL LO• + OH– + M(n+1)+
H
ab
str
n ac
C=C Addition
io
Re
s tio
is n
tion
co
Aldehydes Sc
m
liza
LOH + L•
bi
Alkanes,
na
Cyc
Oxo cmpds,
tio
n
Scission radicals• Epoxides Polymers Peroxides, ketones
(Hydroxy-,
hydroperoxy- )
Secondary oxidations
Schaich, Bailey’s Industrial Fats and Oils, 6th Ed. Vol 1, 2005 www.kemin.com/assurance
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Problem #4 – The Fat Extraction Step
There is no official method for fat extractions for lipid oxidation
analysis.
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Common Extraction Methods
Extraction Solvent Co-Modifiers Processing Evaporation
Cold Petroleum Ether Ethanol Mix sample Rotovap
Hexane Methanol with solvents Nitrogen Evap
Heptane Chloroform for X minutes Vacuum Evap
Chloroform Acetone
Cyclohexane
Ethyl Acetate
Diethyl ether
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Why not use AOAC Official Method
920.39 Ether Extract in Animal Feed?
Method Steps
1. Dry 2 g sample using AOAC Method 934.01 to constant
weight at 95-100 C under pressure of 100 mm Hg or lower
for 5 hours.
2. Soxhlet extract the dried 2 gram sample using anhydrous
ether. Extraction period may vary from 4 hours to 16 hours.
3. Dry extract (fat) for 30 minutes at 100 C.
Oxygen
Heat
Time
Light
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Quantum Mechanics
Heisenberg’s uncertainty principle…
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Quantum Mechanics
Heisenberg’s uncertainty principle…
The uncertainty principle says that we cannot measure the position (x)
and the momentum (p) of a particle with absolute precision. The more
accurately we know one of these values, the less accurately we know the
other.
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Quantum Mechanics
Heisenberg’s uncertainty principle…
The uncertainty principle says that we cannot measure the position (x)
and the momentum (p) of a particle with absolute precision. The more
accurately we know one of these values, the less accurately we know the
other.
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Quantum Mechanics
Heisenberg’s uncertainty principle…
The uncertainty principle says that we cannot measure the position (x)
and the momentum (p) of a particle with absolute precision. The more
accurately we know one of these values, the less accurately we know the
other.
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Quantum Mechanics
Heisenberg’s uncertainty principle…
The uncertainty principle says that we cannot measure the position (x)
and the momentum (p) of a particle with absolute precision. The more
accurately we know one of these values, the less accurately we know the
other.
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http://fprfalliance.agsci.colostate.edu
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Lipid Oxidation Team Goals
1. Identify best PV methods.
2. Standardize industry around methods.
3. Utilize best practices such as sampling.
4. Identify methods that could supplement or potentially
replace the PV measurement in the future.
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Week of April 1st PV Study
• Completed week of April 1st at Tyson’s laboratory.
• Industry wide participation. Multiple rendering, pet
food manufacturers and industry vendors were
involved.
• Range of protein meals such as chicken meal, duck
meal, ovine meal, low ash chicken meal, chicken by-
product meal, fish meal, salmon meal, and kangaroo
meal.
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Week of April 1st PV Study – Task 1
• Eight Commercial Labs also received a few samples
including:
- Eight protein meal samples were sent for analysis.
- One sample was split 5 ways for a repeatability study
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Commercial Lab Sample Results
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Commercial Lab Sample Results
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Commercial Lab Repeatability Study
Overall Average PV = 12.58 Overall Rel STD = 14.5%
AVG = 10.9 Rel STD % = 9.9% AVG = 20.8 Rel STD % = 9.6%
AVG = 13.2 Rel STD % = 6.3% AVG = 6.6 Rel STD % = 28.4%
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Commercial Lab Repeatability Study
Overall Average PV = 12.58 Overall Rel STD = 14.5%
AVG = 10.3 Rel STD % = 11.0% AVG = 10.4 Rel STD % = 28.2%
AVG = 14.0 Rel STD % = 19.1% AVG = 14.6 Rel STD % = 3.5%
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Week of April 1st PV Study – Task 2
• Multiple PV methods were testing on each sample.
- Saftest – AmeriPac
- Camlin – Anisidine Value
- Quartz Analytics – CDR Foodlab
- Tyson Extracted Fat PV Method
- Tyson Extracted Fat PV Method with Autotitrator
- Kemin – FOX II PV Method
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Chicken Meal Repeatability – Summary
Sample AOAC Manual Red - Auto CDR
Description Matrix Titration Titration Fox II SafTest FoodLab
Sample 1 average 4.2 4.2 2.7 4.2 1.6
STDEV 1.3 1.3 0.4 5.3 0.4
Rel STDEV % 31.1 31.8 15.5 126.9 22.9
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I hate PV’s.
I give up!
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Five Stages of Grief
1. Denial
2. Anger
3. Bargaining
4. Depression
5. Acceptance
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Five Stages of Grief with PV Methods
1. Denial
2. Anger
3. Bargaining
4. Depression
5. Acceptance
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Five Stages of Grief with PV Methods
1. Denial that the PV method isn’t perfect.
2. Anger
3. Bargaining
4. Depression
5. Acceptance
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Five Stages of Grief with PV Methods
1. Denial that the PV method isn’t perfect.
2. Anger that the issue must just be your lab that can’t run the test right
3. Bargaining
4. Depression
5. Acceptance
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Five Stages of Grief with PV Methods
1. Denial that the PV method isn’t perfect.
2. Anger that the issue must just be your lab that can’t run the test right
3. Bargaining that maybe the lab must have a new guy running the test
4. Depression
5. Acceptance
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Five Stages of Grief with PV Methods
1. Denial that the PV method isn’t perfect.
2. Anger that the issue must just be your lab that can’t run the test right
3. Bargaining that maybe the lab must have a new guy running the test
4. Depression when realizing all labs give different results
5. Acceptance
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Five Stages of Grief with PV Methods
1. Denial that the PV method isn’t perfect.
2. Anger that the issue must just be your lab that can’t run the test right
3. Bargaining that maybe the lab must have a new guy running the test
4. Depression when realizing all labs give different results
5. Acceptance when realizing the PV test isn’t perfect.
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Where do we go from here?
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Building Blocks from the Pet Food Alliance Trial
1. The Autotitrator reduced the RSD % compared to manual titration.
FOX II had the lowest RSD %.
Sample AOAC Manual Red - Auto CDR
Description Titration Titration Fox II SafTest FoodLab
Sample 1-3 26.4 15.4 12.2 33.6 13.6
2. FOX II had similar results as the extracted fat tests with no outliers.
AOAC Auto
Titration w/ORP AOAC Manual
Probe Titration Fox II SafTest CDR FoodLab
average PV 15.13 14.40 14.67 27.80 23.12
# of Outliers 0 0 0 22 3
3. Data showed that the SafTest system issues comes from the
dilution step. MP Biomedical
4. The CDR Foodlab performed better than the SafTest system.
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Next Steps
1. Need to standardize on a “gold standard” PV method including
a standardized extraction method.
2. Identify acceptable rapid methods that can be utilized when the
“gold standard” isn’t appropriate or needed.
3. Even if a “gold standard” PV method is implemented, it’s an
imperfect test so additional work is needed to develop better
methods (ie BJ Bench was looking at SFE to extract the fat
instead of using solvents)
4. Trust and use of methods beyond PV’s are needed.
5. Total Oxidation Pathway Concept
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Recommended - Multi-Analysis Approach
Primary Secondary
Oxidation Oxidation
Resistance
Antioxidant
to
Residuals
Oxidation
2.00
1.00
0.00
0.0 20.0 40.0 60.0 80.0
Decadienal
n
a tio
hν ∆ Mn+
liz
Scission
yc
C
HO• + •OL LO• + OH– + M(n+1)+
H
ab
n str
ac
C=C Addition
io
Re
s tio
is n
tion
co
Aldehydes Sc
m
LOH + L•
liza
bi
Alkanes,
na
Cyc
Oxo cmpds,
tio
n
LOO● EPR/ESR
Aldehydes GC
Schaich, K.M. Challenges in Elucidating Lipid Oxidation Mechanisms, AOCS. Press 2013. pg. 6 www.kemin.com/assurance
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THANK YOU
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