Transfer of pesticides from commodities to natural
flavors and aroma chemicals
Ian Ronningen
Chem 4101
December 9, 2011
Flavors and Fragrances
•
Aroma chemicals are extracted from commodities through a
number methods
•
Mechanical pressing
•
Solvent extraction
•
Distillation
•
Expression
• These extracts are commonly concentrated and then sold as
fragrances or flavors
Atrazine
Warfarin
Diazinon
Hypothesis



Extraction processes commonly used to
separate flavors and aroma chemicals
from commodities also extract pesticides
Extracted pesticides could make their way
to consumers either through foods
(flavors) or fragrances (aroma chemicals)
Orange, Source of
Expressed orange oil(1)
Pesticides present have the potential to
pose either a chronic or acute health risk
Potential Final
Application (2)
1. Muzaurieta, Annie Bell. "Vitamin C Foods." The Daily Green. Web. 4 Dec. 2011
2. "OMG! Cookies." Poached Prose. Web. 04 Dec. 2011. <http://poachedprose.wordpress.com/2010/08/02/omg-cookies/>
Relevance

Borneo Rainforest(1)


Alachor
To gain a competitive advantage flavor
houses are increasingly sourcing rare
commodities which come from countries
that generally have less regulation
surrounding pesticides
Commodity testing is limited, and screens
limited number of pesticides. Screening
focus is towards pesticides used in the
United States.
If any pesticide ended up harming a
consumer the producer of the food or
fragrance would see massive economic
backlash
1. Borneo Rainforest - Borneo Malaysia." Online Travel Guides of Travel Destinations -. Destination 360.
Analytical Techniques
Separation
Technique
Positive
Negative
HPLC
High sample throughput, numerous
separation mechanisms, large variety
of samples analyzed, AOAC sample
preparation (QueChers)
High solvent costs, co-elution an issue,
GC
Moderate sample throughput, high
resolution, numerous separation
mechanisms
Derivatization maybe required, sample
preparation may be laborious, thermal
degradation is possible
CE
Good separation, resolution can be
made high, small sample size
Poor selectivity for similar analytes,
may require numerous separations of
one sample
Detection Methods
Method
Positive
Negative
Mass
Spectrometry
(triple-quad)
Established libraries, highly
Expense, sensitivity may be low without
selective, sensitivity adequate concentration step
for expected concentration
Flourescence
High sensitivity
Low selectivity, some compounds may
need to be derivitized, no library available
HPLC-MS/MS Analysis
Sample
Preparation
• Quechers SPE
Cartridge
Separation
Analysis
• Waters Acquity
UPLC System
• Waters BEH C18
(2.1 x 100 mm)
• Waters XEVO
TQD Mass
Spectrometer
• High sample throughput, automated, rapid analysis, ability to
deal with complex matrices
• Mass Spectrometer has high analytical selectivity
• Established Mass Spectra Libraries simplifies data analysis
• Many stationary phases available for wide application
• C18 is a good starting point, Phenyl Hexyl also an option
• Online SPE Also an option for higher sample throughput
Experimentation
Incoming
Commodities
Washing
Sample and
analysis
Sample and
analysis
Extraction
Final Product
Sample and
analysis
Sample and
analysis
Addition of internal standards of phenolic butyl-parabens
Control Experiments:
• Sample organic or hydroponic commodities (for incoming and extraction, and final
product)
• Sample unused wash water
"15 Eccentric Endangered Trees, Plants, and Flowers | WebEcoist." WebEcoist. Web. 07 Dec. 2011
"Citrus Processing." Triowin. Web. 07 Dec. 2011
HPLC-MS/MS Analysis
Sample preparation
and clean up
Sample
Separation and
characterization
Restek QuEChERS sSPE
tubes are an AOAC
Method for Prep.
Available (1,2).
Include:
• C18, MGSO4, PSA,
GCB
1.
2.
3.
• Reference to established
libraries
• Unidentified peaks will be
further investigated
Morphed, James, and Peter Hancock. “A RAPID METHOD FOR THE SCREENING AND CONFIRMATION OF OVER 400
PESTICIDE RESIDUES IN FOOD“ Waters Application Notes. Tech. Waters, 2008. Web. 1 Dec. 2011
AOAC Official Method 2007.01, Pesticide Residues in Foods by Acetonitrile Extraction and Partitioning with
Magnesium Sulfate
QuEChERS-A Mini-Multiresidue Method for the Analysis of Pesticide Residues in Low-Fat Products. ResTek Application Notes.
HPLC-MS/MS Concept
HPLC
Separation of compounds from matrix based
off interaction of compounds with stationary
and mobile phases
Diagram of Separation (1)
Mass Spectrometer
Ionization of analytes happens at the source,
MS can either be used to scan or it can be
operated in MS/MS utilizing collision cell and
second quadrapole to analyze fragmentation
patterns
Diagram of Triple-quad (2)
1.
2.
“HPLC Separation Modes” Waters Application Notes, Waters Corporation. 2011.
“Mass Spectrometry Introduction." Department of Chemistry , University of Pittsburgh.
Figures of Merit
Figure
Level
Expected analyte
concentration after SPE
1-500 ppm
Desired Limit of detection*
10 ppb
Xevo TQD limit of detection (1)
0.2 ppb
Required Accuracy*
1-2 ppb
*Figure and requirements depends on the analyte, since
instrument response and level in extract is dependent on
pesticide
(1)Xu, Y. "Simultaneous Determination of Flonicamid and Its Metabolites in Vegetables Using QuEChERS and Reverse-Phase Liquid
Chromatography Tandem Mass Spectrometry." Journal of chromatography. (2011).
Summary
• Sampling along the line of extraction of aroma
chemical from commodities will allow investigation of
safety of these products
• HPLC-MS/MS Analysis allows for effective separation
of pesticides from complex matrix and effective
analysis of pesticides in natural flavors and fragrances
extracted from commodities
• Although added cost of a MS/MS instrument is high
added selectivity and sensitivity justify cost
Additional References
•
AOAC Official Method 2007.01, Pesticide Residues in Foods by Acetonitrile Extraction and
Partitioning with Magnesium Sulfate.
•
Culliney, T W. "Pesticides and natural toxicants in foods." Agriculture, ecosystems &
environment 41.3-4 (1992):297-320
•
Davies J, Barquet A, Vaclavek C, et al. Human Pesticide Poisonings by a Fat-Soluble
Organophosphate Insecticide. Archives of Environmental Health. December 1975;30(12):608.
•
Picó, Y. "Environmental and food applications of LC–tandem mass spectrometry in
pesticide‐residue analysis: An overview." Mass spectrometry reviews 23.1 (2003):45.
•
Reineccius, Gary. Flavor Chemistry and Technology. Boca Raton : Taylor & Francis, c2006.
•
Schreiber, A. "Application of spectral libraries for high-performance liquid chromatographyatmospheric pressure ionization mass spectrometry to the analysis of pesticide and explosive
residues in environmental samples." Journal of chromatography 869.1-2 (2000):411
•
Seiber, J N. "Contributions of Pesticide Residue Chemistry to Improving Food and
Environmental Safety: Past and Present Accomplishments and Future Challenges." Journal of
agricultural and food chemistry 59.14 (2011):7536-7543.
•
Thurman, E M. "Choosing between atmospheric pressure chemical ionization and electrospray
ionization interfaces for the HPLC/MS analysis of pesticides." Analytical chemistry 73.22
(2001):5441.