Post on 04-May-2022
Food analytics & quality control
Quality Requirements and
Analytics of Beeswax
Jürgen Hauck
Research and Development
China Bee Products Industry Concerence 2019, Kunming, China
Overview
Laboratory FoodQS
Production and Composition of Beeswax
Beeswax as a commercial product
Authenticity
o Requirements
o Analysis and Results
Residues
o Requirements
o Analysis and Results
March, 5th-6th, 2019 FoodQS GmbH 1
Total Hydrocarbons
Waxvalues
Water
Pollution
Residues
- Pesticides
- Antibiotics
ForeignParaffins
Stearin Wax
Dropping& melting
pointHeavy metals
March, 5th-6th, 2019 FoodQS GmbH 2
FoodQS – more than 20 years experience in analysis of honey and bee products
GMO
Type ofhoney
Residues
- Pesticides
- Antibiotics
Chem.-phys.
Parameter
Adulteration
- Syrup Marker
- Oligosaccarides
- Foreign enzymes
- Isotopes
Contaminants
-Alkaloide
-Heavy metals
Beeswax- Production and Composition
1) Bienen &Natur 10/2007 2)Bee product science, April 2016 3) Neumann, STUA Aulendorf 2017
Production
By 12-18 day old worker bees
Wax glands at abdomen of bees3)
Liquid wax congeals to platelets
One platelet about 0.8 mg 3) more than 106 platelets for 1kg wax
About 6 kg honey is needed 1)
Maximum is produced during growth phase of bee colony
Moderate climate between april and june
Sugar to wax ratio: from 3:1 and 30:1 2)
www.imkereikolonko.de
35%
14%14%
12%
8%
6%
March, 5th-6th, 2019 FoodQS GmbH 3
Beeswax- Production and Composition
1) TULLOCH, A P (1980) Beeswax - Composition and analysis. Bee World 61 (2): 47-62.
www.imkereikolonko.de
Monoester
Diester
Triester
Hydroxy monoester
Hydroxy polyester Acid esters
Acid polyesters
Hydrocarbons
Free acids
Alcohols
others
Composition 1)
35%
14%
14%
12%
8%
6%
March, 5th-6th, 2019 FoodQS GmbH 4
Beeswax- A commercial product
• Plasticisers, Emulgator, Filming agents
• Texture forming agents in cremes, lotionsCosmetics
• coating agents & surface treatment product
• chewing gum baseFood Processing
Food Additive (E901)
• Glacing agent for tablets and pastilles
• consistency enhancer for ointment and tincturesPharma
• Glacing agent and sealent in shoe- and leatherPolishTechnical Use
Candle industry Beekeeping industry
March, 5th-6th, 2019 FoodQS GmbH 5
Beeswax- A commercial product
1) www.indexbox.co.uk 2) FAOSTAT2005 3) EPOPA/FAOSTAT 2005
USA Central AfricaEthiopia
Ivory CoastAustralia
UkraineTanzania
Argentina
China
Imports of beeswax from countries outside the EU 3)
-12000
-8000
-4000
0
4000
8000
12000
ton
es
World trade in Beeswax 2003 2)
Export Import
2003
0
50
100
150
200
250
0
25
50
75
100
125
150
175
200
2007 2008 2009 2010 2011 2012 2013 2014
%
mill
ion
USD
Global Beeswax Exports 1)
Export (million USD) to previous year (%)
0
50
100
150
200
250
0
25
50
75
100
125
150
2007 2008 2009 2010 2011 2012 2013 2014
%
mill
ion
USD
Global Beeswax Imports 1)
Import (million USD) to previous year (%)
March, 5th-6th, 2019 FoodQS GmbH 6
Beeswax- A commercial product
2003
Increasing demand
Limited availability of natural beeswax
Increasing Price
Potential target of adulteration!
March, 5th-6th, 2019 FoodQS GmbH 7
Authenticity
Cosmetic and Pharma industry: European PharmacopoeiaTests
Characters Sensorial and solubility analysis
Relative density About 0.960
Drop point 61-66 °C
Acid value 17-22 (17-24 for bleached beeswax)
Ester value 70-80
Saponification value 87-102 (87-104 for bleached
beeswax)
Ceresin, paraffin and certain other
waxes
max. 65 °C
Glycerol and other polyols max. 0.5 %
Similar specifications in other Pharmacopoeia (USP, JP, British) 1) www.deutscher-apotheker-verlag.de
March, 5th-6th, 2019 FoodQS GmbH 8
Authenticity
Food industry: European regulation 231/2015Tests
Characters Sensorial and solubility analysis
Relativ density About 0.960
Melting range 62-65 °C
Acid value 17-24
Saponification value 87-104
Peroxid value max. 5
Ceresin, paraffin and certain other
waxes
max. 65 °C
Glycerol and other polyols max. 0.5 %
Fats, Japan wax, rosin and soaps no precipitate
1) www.foodhealthlegal.com
March, 5th-6th, 2019 FoodQS GmbH 9
Authenticity
Candle industry: RAL-GZ041
Tests
Drop point 61-65 °C
Relativ density About 0.960
Acid value 17-24
Saponification value 87-104
Ester value 70-80
Relation value 3.3-4.3
Total hydrocarbons max. 18 %
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Authenticity: Results
Target Value
61-66 °C
Target Value
62-65 °C
Target Value
about 0.96Target Value
as low as possible
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Authenticity: Results
Target Value: 17-24 Target Value: 87-104 Target Value: 70-80 Target Value: 3.3-4.3
March, 5th-6th, 2019 FoodQS GmbH 12
Authenticity
Candle industry: RAL-GZ041
Tests
Drop point 61-65 °C
Relativ density About 0.960
Acid value 17-24
Saponification value 87-104
Ester value 70-80
Relation value 3.3-4.3
Total hydrocarbons max. 18 %
1) JECFA: Chemical and Technical assessment: Beeswax 2) Bonvehi and Bermejo, 2012 3) Tulloch and Hofmann, 1972
Total Hydrocarbons in Beeswax (Literature): 11.6-17.7% 1), 2), 3)
March, 5th-6th, 2019 FoodQS GmbH 13
Addinginternal
standards
Solvent extraction
Derivatization
GC-FIDAnalysis
Authenticity: State-of-the-Art Analysis: GC
1) www.amazon.de 2) www.online-shop.eppendorf.de 3) www.biosystems.ch 4) www.sciex.com 5) www.thermoscientific.com
March, 5th-6th, 2019 FoodQS GmbH 14
Authenticity: Results
authentic Beeswax Paraffin adulterated Beeswax
Paraffin/Ceresin
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Authenticity: Results
Authentic
Beeswax
Stearin Wax
Adulterated
Beeswax
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Stearic acid
Palmitic acid
Authenticity: Results
67%
33%
Beeswax samples (N=960)
authentic adulterated with paraffin (>1%)
March, 5th-6th, 2019 FoodQS GmbH 17
0
10
20
30
40
50
60
70
80
Nu
mb
ero
fsa
mp
les
Adulterated samples with Paraffin
1-5 % 5-10% 10-15% 15-30% 30-50%
Authenticity: Results
94%
6%
Stearic acid (N=960)
authentic
adulterated
96%
4%
Palmitic acid (N=960)
authentic
adulterated
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Residues and contaminants
Cosmetic and Pharma industry: European Pharmacopoeia (9.0)
Azinphos-methyl 1 mg/kg Fluvalinate 0.05 mg/kg
Aldrin and Dieldrin (sum of) 0.05 mg/kg Heptachlor (sum of heptachlor, cis
and trans isomers of
heptachlorepoxid)
0.05 mg/kg
Brompropylate 3 mg/kg Hexachlorbenzol 0.1 mg/kg
Chlorfenvinphos 0.5 mg/kg Lindan 0.6 mg/kg
Cyfluthrin (sum of) 1 mg/kg Malathion and Malaoxon (sum of) 1 mg/kg
Cypermethrin (sum of) 1 mg/kg Mirex 0.01 mg/kg
Dimethoate and Omethoate (sum of) 0.1 mg/kg Permethrin and isomers (sum of) 1 mg/kg
DDT (sum of o,p‘-DDE, p,p‘-DDE,
o,p‘-DDD, p,p‘-DDD, o,p‘-DDT, p,p‘-
DDT)
1 mg/kg Phosmet 0.05 mg/kg
Fenvalerate 1.5 mg/kg Piperonyl butoxide 3 mg/kg
BUT: some active substance, important in beekeeping, are missing in the spectrumCoumaphos, Flumethrin, Amitraz respectively DMF
March, 5th-6th, 2019 FoodQS GmbH 19
Residues and contaminants
Beekepers and beeswax industry: Spectrum of relevant pesticides and varroacides
Varroacides (e.g. Brompropylat, Fluvalinat, Coumaphos, Flumethrin, Amitraz) 0.5 mg/kg*
Varroacide: Thymol 3 mg/kg
Neonicotionides (e.g. Thiacloprid, Imidacloprid) 0.5 mg/kg
Pesticides (e.g. Vinclozolin, Myclobutanil, Tolylfluanid) 0.5 mg/kg*
Pyrethroides (e.g. Cyfluthrin, Cypermethrin, Permethrin) 0.5 mg/kg*
Wax moth treatment: Paradichlorobenzene 0.5 mg/kg*
Insect repellent: Diethyltoluamid (DEET) 0.1 mg/kg
* Experiments Dr Wallner, University of Hohenheim:
Incubation of honey with beeswax containing different concentrations of residues
Result: At 1 mg/kg residue in beeswax, a migration of pesticides into honey could beobserved
March, 5th-6th, 2019 FoodQS GmbH 20
Residues and contaminants
Candle industry: RAL-GZ041
Lead max. 0.1 mg/kg
Food industry: European regulation 231/2015
Arsenic max. 3 mg/kg
Lead max. 2 mg/kg
Mercury max 1 mg/kg
1)
1) www.thermofisher.com2) www.cem.deMarch, 5th-6th, 2019 FoodQS GmbH 21
Addinginternal
standards
Solvent extraction
Clean-up
Analysis
LC-MS/MS
GC-MS/MS
Residues and contaminants in beeswax
1) www.amazon.de 4) www.sciex.com2) www.online-shop.eppendorf.de 5) www.thermoscientific.com3) www.biosystems.ch
March, 5th-6th, 2019 FoodQS GmbH 22
Residues and contaminants in beeswax
Inte
nsi
ty [
cps]
Time [min]
Azoxystrobin
Inte
nsi
ty [
cps]
Time [min]
Piperonylbutoxid
Inte
nsi
tiy
[cp
s]
Time [min]
DEETIn
ten
sity
[cp
s]
Time [min]
Fluvalinate
Inte
nsi
ty [
cps]
Time [min]
Coumaphos
Inte
nsi
ty [
cps]
Time [min]
Permethrin Isomers
March, 5th-6th, 2019 FoodQS GmbH 23
Residues and contaminants in beeswax: Results
#150%
#227%
#313%
#46%
#53%#6
1%
Number of Residues
March, 5th-6th, 2019 FoodQS GmbH 24
45%
55%
Total Samples (N=274)
Negativ (< 0.2 mg/kg) Positiv (> 0.2 mg/kg)
Residues and contaminants in beeswax: Results
0
20
40
60
80
100
120
Nu
mb
er o
f p
osi
tive
Sam
ple
s
Pesticides
March, 5th-6th, 2019 FoodQS GmbH 25
Residues and contaminants in beeswax: Results
97%
3%
1,4-Dichlorobenzene (N=214)
<0.1 mg/kg >0.1 mg/kg
66%34%
Thymol (N=213)
<0.75 mg/kg >0.75 mg/kg
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Residues and contaminants in beeswax: Conclusion
Adulteration Different requirements (Ph Eu, RAL-GZ041, EU specification)
GC analysis
o more sensitive and precise than conventional analytics
o Adulteration with Paraffin more possible than with Stearin
Residues Maximum residues depends on purpose of beeswax
o Beekeeping: 500 ppb
o Cosmetic/ Pharma industry: different MRL: 10-3000 ppb
Most detected residues: Fluvalinate, Coumaphos and Permethrin
Varroacide Thymol: up to 150 ppm
March, 5th-6th, 2019 FoodQS GmbH 27
The End
Thank you very much
for your attention!
March, 5th-6th, 2019 FoodQS GmbH 28