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Honey Authenticity

1. Honey origin (floral & geographical)

2. Honey adulteration
Honey Authenticity

PPP-Indien/Quality Control.

QSI 2013

QSI 2012

1. Honey origin

Honey Authenticity

QSI 2013

Honey origin determination of pollen spectrum


microscopical pollen count
test combined with examination of flavor and electrical conductivity

pro
information about geographical and botanical origin with one single test
furthermore overview about possible fermentation, adulteration, contamination etc.

con
only performable by staff with considerable experience
does not work for filtered honey (or mixtures of filtered and unfiltered honeys)

Honey Authenticity

QSI 2013

Honey origin trace elements


determination of trace elements with ICP-MS or AAS

pro
besides determination of origin additional information about toxic heavy metals

con
large databases are required for evaluation
at least 20 different elements necessary complex statistical evaluation
strong impact on the composition of elements by nearby industry
expensive test due to costly instrumentation

Honey Authenticity

QSI 2013

Honey origin isotope ratios


determination of different isotope ratios (e.g. hydrogen, oxygen,
nitrogen, sulphur)

pro
-

con
large databases necessary (difficult to available)
expensive test due to costly instrumentation

Honey Authenticity

QSI 2013

2. Honey adulteration

Honey Authenticity

QSI 2013

Honey adulteration
Addition of sugars to honey
Feeding of sugars to bees
Addition of pollen
Addition of filtered honey

Honey Authenticity

QSI 2013

Honey adulteration 13C/12C-Isotope Ratio-MS


determination of carbon isotope ratios of honey and honey protein
detection of added sugars from C4-plants
Note: traces of bee feeding stuff is possibly not avoidable

pro
covers all sugars from C4-plants, e.g. corn ( high fructose corn syrup) and sugar
cane
foreign sugars are quantified accurately (limit: 7 %)
AOAC Official Method 998.12, worldwide approved and accepted
sugars from C3-plants could be detected, too (example: rice syrup, beet sugar)

con
sugars from C3-plants detectable in higher amounts, but no quantification possible
Honey Authenticity

QSI 2013

Honey adulteration QSI-statistics for 13C/12C-IRMS


100,00%
90,00%
80,00%

2007

70,00%

2008

60,00%

2009

50,00%

2010

40,00%
30,00%
20,00%
10,00%
0,00%

C IRMS honey incl. protein


2007 to 2012
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Honey Authenticity

2011

2012
2011
2010
2009
2008

2012

2007
</=7

>7

QSI 2013

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Honey adulteration 13C/12C-IRMS positive


differences
Official AOAC interpretation: detection of sugars from C4-plants =
negative differences between 13C-results of protein and honey
research results by QSI:
high positive differences (> 1.2 ) indicate the presence
of sugars from C3-plants
evaluation of >1000 commercial honey samples
results largely confirmed by alternative tests
published at AOAC Annual Meetings in 2008 and 2011
aim: modification of interpretation of AOAC Official Method 998.12

Honey Authenticity

QSI 2013

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Honey adulteration LC-13C-IRMS


determination of carbon isotope ratios of single sugar fractions
Use of e.g. inverted beet sugar syrup (=C3) to blend honey, and
addition of C4-fructose to increase F/G-ratio > 13C-results of fructose
and glucose differ from each other

pro
some syrups mixed of C3 and C4 can possibly be detected

con
determination of pure C4- or C3-sugars not possible
Results honey study QSI: 13C-results of single sugar fractions differ considerably in
freshly collected acacia nectars high natural variations possible
Honey Authenticity

QSI 2013

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Honey adulteration sugar profile


HPLC-RI determination of specific mono-, di- and trisaccharides
indications for adulteration:

high amounts of sucrose (possible origin: beet or cane sugar)


high amounts of maltose and maltotriose (possible origin: starch-based syrup)
low F/G-ratio (possible origin: inverted sugar syrup)

pro
many information with one single test

con
all indications mentioned above can occur naturally in honey, depending on the type
confirmation required
no quantification of foreign sugar
Honey Authenticity

QSI 2013

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Honey adulteration oligosaccharide profile


HPLC-PAD determination of oligosaccharides in order to detect
additions of starch-based sugar syrups
long experience: method developed and published by QSI 20 years
ago

pro
covers all starch-based syrups, independent from carbon isotopes
sensitive test, detection limit about 0.1 - 1 % added syrup (BUT: such low amounts
could possibly not be technically avoidable after feeding the bees)

con
no quantification possible due to high variations of oligosaccharides in different syrups,
depending on the origin and the treatment of the syrup
Honeydew honeys contain oligosaccharides naturally, which need to be distinguished

Honey Authenticity

QSI 2013

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Dextrin-standard (Dextrin from


potatoes)
Honey Authenticity

QSI 2013

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Authentic honey sample


Honey Authenticity

QSI 2013

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Authentic honey sample intentionally


adulterated with 50 % starch-based syrup
Honey Authenticity

QSI 2013

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Starch-based syrup
Honey Authenticity

QSI 2013

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Adulterated honey sample

Honey Authenticity

QSI 2013

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Honey adulteration beet sugar adulteration


NEW METHOD, offered by QSI since April 2013
determination of a specific marker substance for beet sugar with LCMS/MS
mainly positive findings in honeys from China and Eastern Europe

pro
high specific test, substance only occurs in beet sugar syrup
positive findings even when inverted beet sugar is added to honey

con
no quantification possible due to high variations of the marker substance in different
syrups, mainly depending on the treatment of the syrup

Honey Authenticity

QSI 2013

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Honey adulteration rice syrup adulteration


determination of a specific marker substance for rice syrup
R) with LC-MS/MS

(SM-

pro
high specific test, substance only occurs in rice syrup

con
no quantification possible due to high variations of the marker substance in different
syrups, mainly depending on the treatment of the syrup

Honey Authenticity

QSI 2013

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Honey adulteration trace marker for rice syrup


(TM-R)
determination of arsenic
background: rice plants enrich arsenic from the ground.
findings in honey >0.01 mg/kg indicate addition of rice syrup
only recommended for confirmation of doubtful results with other
analyses

pro
-

con
depending on the soil conditions and treatment of the syrup, the amounts of arsenic
vary considerably unreliable results
Honey Authenticity

QSI 2013

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Honey adulteration foreign invertase


determination of the activity of beta-fructofuranosidase:
enzyme which does not occur in honey naturally
used to invert sucrose to glucose and fructose
indirect proof for the addition of beet sugar syrup

pro
high specific test

con
no quantification of added sugar possible
if inversion is carried out in another way and/or if the enzyme is destroyed after
inversion negative results in spite of adulteration with beet sugar
Honey Authenticity

QSI 2013

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Honey adulteration foreign amylase


determination of the activities of beta- and gamma-amylase:
enzymes which do not occur in honey naturally
used to produce sugar syrup from starch
indirect proof for the addition of starch-based syrups

pro
-

con
no quantification of added sugar possible
same as foreign invertase: if inversion is carried out in another way and/or if the
enzymes are destroyed after inversion negative results in spite of adulteration
Honey Authenticity

QSI 2013

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Honey adulteration further tests


pollen spectrum
as mentioned at the beginning: overview about possible
adulteration
foreign dextrines
two alternative methods (Fellenberg, Fiehe) to detect
oligosaccharides in honey
only applicable for amounts >5 %
proline
honey-typical amino acid
amounts < 180 mg/kg indicate addition of foreign sugar
Honey Authenticity

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Our recommendation to detect honey adulteration


pollen spectrum

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overview about irregularities

C/12C-IRMS, Code 40260

covers all sugars from C4-plants (cane, corn etc.) and even
possibly from C3-plants

oligosaccharide profile, Code 40290

covers all starch-based sugar syrups

LC-MS/MS test for beet sugar, Code 40470

covers adulteration of (inverted) beet sugar

Honey Authenticity

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Thank you for your attention!


Quality Services International GmbH
Am Flughafendamm 9a
D-28199 Bremen
Fon: +49 421 594770
info@qsi-q3.de
www.qsi-q3.de

Honey Authenticity

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