quality requirements and analytics of beeswax

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


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%


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%


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



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 (%)



2003

Increasing demand

Limited availability of natural beeswax

Increasing Price

Potential target of adulteration!


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


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


Authenticity

Candle industry: RAL-GZ041

Tests



Acid value 17-24


Ester value 70-80

Relation value 3.3-4.3

Total hydrocarbons max. 18 %


Authenticity: Results

Target Value

61-66 °C

Target Value

62-65 °C

Target Value

about 0.96Target Value

as low as possible



Target Value: 17-24 Target Value: 87-104 Target Value: 70-80 Target Value: 3.3-4.3


Authenticity


Tests



Acid value 17-24


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)


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



authentic Beeswax Paraffin adulterated Beeswax

Paraffin/Ceresin



Authentic

Beeswax

Stearin Wax

Adulterated

Beeswax


Stearic acid

Palmitic acid


67%

33%

Beeswax samples (N=960)

authentic adulterated with paraffin (>1%)


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%


94%

6%

Stearic acid (N=960)

authentic

adulterated

96%

4%

Palmitic acid (N=960)

authentic

adulterated


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



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




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


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


Residues and contaminants in beeswax: Results

#150%

#227%

#313%

#46%

#53%#6

1%

Number of Residues


45%

55%

Total Samples (N=274)

Negativ (< 0.2 mg/kg) Positiv (> 0.2 mg/kg)


0

20

40

60

80

100

120

Nu

mb

er o

f p

osi

tive

Sam

ple

s

Pesticides



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


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


The End

Thank you very much

for your attention!


quality requirements and analytics of beeswax

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