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Contamination of teas and herbal infusions – a current review of

findings for pyrrolizidine alkaloids and further contaminants

Eurofins Dr. Specht Laboratorien GmbH

Johannes Jaschik

CoTeCa 2018

Contaminants ABC

Anthraquinone Biphenyl, Bromide Chlorate, Copper Diethyltoluamid (DEET) Ethoxyquin Folpet, Fluoride G… Hexachlorobenzene I… J… K… Lead Mercury

2 Johannes Jaschik, COTECA 2018

Nicotine Ortho-Phenylphenol (2-Phenylphenol) Pyrrolizidine alkaloids, Perchlorate, PAHs …

QACs… Rare earth elements Smoke, S421 Trimethylsulfonium, Tallow amines U… V… W… X… Y… Z…

Residues vs. Contaminants

from analytical perspective there is

no difference


Residues: Whatever remains after the

use of use or application of a certain chemical

Contamination: Presence of an unwanted

chemical which not originate of an use in the material.

A residue may act as a contaminant in material or

environment it was not intented to be used in.

Residues vs. Contaminants

Why is it important to differ between residues and contaminants:

• finding the source of the residue/contamination • residues: checking the application (limit/change use)

• contaminants: checking environment (unavoidable?)

• distribution of the residue/contamination • often spot contamination, not equally distributed

• residues are more equally distributed

• maybe different legal requirements • e.g. organic production


Analytical options

How do you approach the assessment of contamination in tea and herbal infusion:

Looking at your product…


There are as many different substances which act as contaminants as products available.

Examples for Categories

Photo initiators


PAHs

Microbiology

Radioactivity

Irradiation

Desinfectans (e.g. QACs)

Plasticizers

Mineral oils (MOSH/MOAH)

Chlorate, Perchlorate, Phosphoric acid, etc. …

Fluoride

Dioxins (illegal) dyes

Vet drugs

Allergenes

GMO

Pesticides

Heavy metals

… and other products in your portfolio

Multi Method

vet drugs Specific methods e.g. microbiology

Offer with different methods

There is no „C.S.I. – analysis“ but quite a lot of specific work!


Multi Method

pesticides

group specific methods

e.g. mycotoxins

Specific methods e.g. heavy metals

sample tea

many different methods, modern equipment,

experience in evaluation

all contaminants known

What Eurofins can offer:

Keeping your risk low


Enjoy your product !

Not to analyse everything

but to control for your risks

and specific checking these.

In order to have time

and opportunity to…

Example Lapsang souchong


Lapsang souchong […], sometimes referred to as smoked tea [..] is a black tea (Camellia sinensis) originally from the mountainous Wuyi region in the Chinese province of Fujian. It is distinct from other types of tea, as the leaves are traditionally smoke-dried over pinewood fires, imparting a distinctive flavor of smoky pine. (Wikipedia, 2018)

THIE Compendium of Guidelines for Tea, 2018

https://en.wikipedia.org/wiki/Black_tea

https://en.wikipedia.org/wiki/Camellia_sinensis

https://en.wikipedia.org/wiki/Wuyi_Mountains

https://en.wikipedia.org/wiki/Fujian

https://en.wikipedia.org/wiki/Smoking_(cooking)

https://en.wikipedia.org/wiki/Pine

Contamination of Lapsang


Biphenyl Anthrachinon

2-Phenylphenol Phthalimid (PI)

Bifenthrin Cypermethrin

Thiamethoxam Cyhalothrin, lambda-

Acetamiprid Thiacloprid

Phthalimid

Anthraquinone

Cypermethrin

Bifenthrin

Imidacloprid

Chlorfenapyr

Thiamethoxam

Acetamiprid

Cyhalothrin, lambda-

Thiacloprid

Carbendazim

Glyphosate

ranking for Lapsang

ranking for all teas

different ranking but more important also

different concentrations

Lapsang contaminants


0,010,020,030,040,050,060,070,080,090,0

Teas except Lapsang

0,010,020,030,040,050,060,070,080,090,0

Lapsang

Anthrachinon

2-Phenylphenol

Phthalimid (PI)

Biphenyl

• completely different concentration

• but each substance has slightly different distribution

• keeping in mind, that Biphenyl/2-Phenyphenol are not

common on Tea except Lapsang at all

Biphenyl (1/2)

Further contaminant from smoke and other sources. In the past used in citrus fruits.


Detection in foodstuff with GC-MS using multi method possible. Products MRLs

Dried chilli 0.01 Dried fruits 0.01 Herbal infusions 0.05 Herbs 0.1 Mate 0.5 Nutmeg/Macis 1 Rice 0.01 Spices 0.05 Tea 0.05

Biphenyl (2/2)


Evaluation for organic products takes into account the different contamination sources of Biphenyl. But if the MRL is exceeded – there is no further tolerance. 0,0

10,0

20,0

30,0

40,0

50,0

60,0

70,0

<=0,01<=0,02<=0,05 <=0,1 <=0,2 <=0,5 >0,5

Biphenyl: overview distribution

conventional

organic

Graph for conventional and organic products comparable – contamination probable. Higher concentrations in mate and nutmeg.

Anthraquinone (1/3)


Detection in foodstuff with GC-MS/MS using multi

method possible.

pesticide

Anthraquinone (2/3)

Products:


0,0

10,0

20,0

30,0

40,0

50,0

60,0

<=0,01 <=0,02 <=0,05 <=0,1 >0,1

Anthraquinone: overview distribution

Conventional

Organic

Products MRLs* Tea 0.02 herbal infusions 0.02 Mate 0.02 packaging material Inks Herbs 0.01 Spices 0.02 dried fruits/vegetables 0.01

Packaging / inks

Graph for conventional and organic products comparable – contamination probable.

*without concentration factor

Anthraquinone – source (3/3)


Smoke

2-Phenylphenol (1/2)


0,0

5,0

10,0

15,0

20,0

25,0

30,0

35,0

<=0,01<=0,02<=0,05 <=0,1 <=0,2 <=0,5 >0,5

2-Phenolphenol: overview distribution

conventional

organicMore than one effect.

Detection in foodstuff with GC-MS using multi method possible.

Now the graph shows the typical curve for contamination


2-Phenylphenol (2/2)

0,05,0

10,015,020,025,030,035,040,045,050,0

<=0,01<=0,02<=0,05 <=0,1 <=0,2 <=0,5 >0,5

2-Phenylphenol: overview (without citrus)

conventional

organic

Products MRLs Citrus /oil 5 Coffee 0,1 Fruits 0,05 Herbal infusions 0,1 Ink / packaging Spices 0,1 Tea 0,1

Contamination source

Approved use Either use, as in citrus fruits, or contamination from packaging/ink or environment (smoke).

Folpet/Phthalimide

19

Phthalimide

Molar Mass: 147,13 g/mol

Folpet

Molar Mass: 296,56 g/mol

Phthalimide residues have to be multiplied by 2 in order to gain the Folpet residue.

Johannes Jaschik, COTECA 2018

Regulation (EC) No 396/2005 as it stood before being amended by this Regulation shall continue to apply to products which were produced before 26 August 2016.

Folpet/Phthalimide Relana/BNN

Considering all arguments including the above mentioned, a positive finding of Phthalimide only is in our oppinion not sufficient to decide if regulation (EC) 396/2005 should be applied in this case.


forming under heating conditions

Folpet/Phthalimide data review


0,05,0

10,015,020,025,030,035,040,045,0

<=0,01<=0,02<=0,05 <=0,1 <=0,2 <=0,5 >0,5

Phthalimide: overview distribution

conventional

organic

Products MRLs Tea 0,1 Spices 0,1 Apple 0,03 Dried Chillies 0,03 Herbal infusions 0,1 other fruits/concentrates 0,03 - 6

Analysis possible with GC/MS(/MS) using multi methods for pesticides but use of isotope marked standards for Folpet and Phthalimide necessary.

Although some use of Folpet (or Captan which contains Folpet additionally) is known, contamination is the prevalent factor of Phthalimide findings.

If Folpet is actively used you can expect Phthalimide in neighbouring fields.

Heavy metals

Plants can take up the heavy metals e.g. lead from the soil and under certain conditions high levels can be accumulated in the leaves and other edible parts of the plant. For tea plants it is known, that they can uptake heavy metals from the soils and a proportion will be transported to the tea leaves which are used for the tea infusion.


Typically detected by single element analysis with AAS or ICP/MS.

“…and some green tea leaves, particularly those from China, are contaminated with lead…”

https://www.researchgate.net/publication/295858621_Metals_Contents_in_Black_Tea_and_Evaluation_of_Potential_Human_Health_Risks_to_Consumers

https://well.blogs.nytimes.com/2013/05/23/whats-in-your-green-tea/

Lead


0,0

5,0

10,0

15,0

20,0

25,0

30,0

35,0

40,0

Lead

conventional

organic

tea tobacco

packaging material herbal infusions

spices

No MRLs for tea and herbal infusions in general, evaluation is only possible for selected commodoties according to regulation 1881/2006 .

Only few data for organic available.

Copper (1/2)


Products with copper concentrations exceeding 10mg/kg

Products MRLs Cocoa 50 Coffee 50 Herbal infusions 100 Herbs 20 Oilseeds 30-40 Spices 40 Tea 40 Tobacco


Plants can take up the heavy metals from the soil and under certain conditions high levels can be accumulated in leaves and other edible parts of the plant.

Copper (2/2)

Evaluation is done accordingly to EU regulation 396/2005.


0,0

10,0

20,0

30,0

40,0

50,0

60,0

70,0

<=0,1 <=0,5 <=2 <=10 <=20 <=40 >40

Copper: overview distribution

conventional

organic

Contamination? Use? Depending on the product. Use of copper is allowed in organic farming.

Mercury (1/2)

Plants can take up the heavy metals from the soil and under certain conditions high levels can be accumulated in leaves and other edible parts of the plant.


Produkte MRLs Tea 0,02 Shrimps 0,5 Herbs 0,01* Herbal infusions 0,02 Spices 0,02 Mushrooms 0,01 Tobacco


Bigger topic in seafood!

Not surprisingly the graph shows a sign for contamination.


Mercury (2/2)

Evaluation for products is done only according regulation 396/2005 with exception of

seafood where the evaluation is done according to contaminant regulation 1881/2006!

0,0

10,0

20,0

30,0

40,0

50,0

60,0

Mercury: overview distribution

conventional

organic

Chlorate / Perchlorate


EPRW 2016

EFSA 2015

BfR 2018

Chlorate (1/3)


Detection in foodstuff with LC-MS/MS using a single method including perchlorate. Products SANTE MRLs

[mg/kg] Milk 0.2

Starch (cereals) 0.04

Tea 0.15

Vegetables 0.01 - 0.7

Fruits 0.015 - 0.03

Herbal infusions 0.15

Herbs 0.6

Coffee 0.15

…

Herbicide effects: destroys oxidative plant tissue Typical byproduct of disinfectants, e.g. used for chlorination of drinking water

• Defined as pesticide

• current toxicological evaluation (PRIMO) high contents are being tolerated

• Draft document for new maximum residue levels SANTE 10684_2015 drastic lowering compared to PRIMO-model

Chlorate (2/3)


This would lead to serious problems with a wide range of foodstuff.

Chlorate (3/3)


Several effects at work. Chlorate is in use and this differently in conventional and organic production and in different products.

0,0

5,0

10,0

15,0

20,0

25,0

30,0

35,0

<=0,01<=0,02<=0,05 <=0,1 <=0,2 <=0,5 >0,5

Chlorate: overview distribution

conventional

organic

Evaluation only according to PriMo regardless of cultivations status.

This residue of Chlorate could be derived from a use of chlorinated resources during production or processing or from the use of chlorinated water due to disinfection purposes. In many countries, a use of chlorinated water is legal and partly statutory to minimize microbiological risks. […]

Based on the current EFSA model PRIMo, the exhaustion of ARfD of 0.036 mg/kg bodyweight in the analyzed sample amounts x %. Therefore, an exceedance of the ARfD-value is not given. Nevertheless, we recommend finding the source of entry and minimize levels of Chlorate in the product.

Perchlorate (1/3)

Exception because it is regulated as contaminant (not defined as pesticide!). However often monitored together with Chlorate.


Detection in foodstuff with LC-MS/MS using a single method including chlorate.

Mainly anthropogenic origin - can occur naturally. Fireworks is suggested to be one source in specific origins.

Not regulated in the pesticide regulation.


Perchlorate (2/3)

Contamination in food but non-food applications/use which lead to punctual high concentrations.

0,010,020,030,040,050,060,070,0

Perchlorate: overview distribution

conventional

organic

Perchlorate (3/3)

There is no specific conclusion for organic products. Perchlorate is treated in every respect as an contaminant.


Fruits Vegetables

Herbs Cereals

Tea Herbal Infusions

Coffee Milk

Spices

Perchlorate findings are sometimes specific for certain origins e.g. China.

Pyrrolizidine alkaloids (PAs)

PAs are produced by more than 6000 flowering plants (protection against herbivores)

Most relevant plant is ragwort (Senecio jacobaea L.)

660 PAs and corresponding N-oxides are known; some of them being extremely toxic

not clear scope: BfR17 – BfR21 – BfR28 – or 35/38 or EFSA17

????


Structures Pyrrolizidine alkaloids (PAs)

36

Retronicine

Senecionine Type

Lycopsamine Type Monocrotaline Type

Lycopsamine, Intermedine, Echimidine,

Lasiocarpine etc.

Senecionine, Senkirkin, Retrorsine,

etc.

Monocrotalin, Jacobine,

Trichodesmine


Background Pyrrolizidine alkaloids (PAs)

Unexpectedly high concentrations of PAs were found in (herbal) tea (0- 3.4 mg/kg dry product) (BfR statement 018/2013)

91 % of (herbal) teas contained PAs, 60 % of nutritional supplements; animal derived products only occasionally contaminanated (EFSA study, 2015, analysis of 1.000 samples)

Affected products are:

37

tea (camellia sinensis) herbs, herbal teas

honey, honey products salad, salad mixtures

flour eggs, meat, milk (by carry-over)


PA Analysis @ Eurofins

Relevance Further to the above mentioned matrices:

pseudocereals, feed, borage oil, nutritional supplements, esp. products for infants, pregnant and nursing women

Continuous consumption of products containing high concentrations of PA is critical for infants, toddlers, pregnant and nursing women (BfR)

Specht Method Existing LC-MS/MS method for

BfR 32 PAs / N-oxides Important: also for GMP requirements


Analytical view on PA

39

Retrorsine: negative in black tea

Seneciphylline N-oxide: added in black tea


Findings PA tea@ Eurofins

• Total number of samples: >4500 (since Jan 2015)

• Results from zero to 10000 µg/kg in black tea

• Main PAs found (in all commodities):

40

Retrorsine-NOx Lycopsamin-NOx Retrorsine Senecionine-NOx Jacobine-NOx Seneciphylline-NOx Senecionine Indicine-NOx + Intermedine-NOx Indicine + Lycopsamine Jacobine Heliotrine-NOx Intermedine Senecivernine-NOx Lasiocarpin-NOx Senkirkine Europin-NOx Heliotrine Seneciphylline Europine N-oxide Lasiocarpine Europin Echimidine Senecivernine Echimidine-NOx


Review findings

41

Europine N-oxide Senecionine-NOx

Heliotrine-NOx Lasiocarpin-NOx Lycopsamin-NOx Retrorsine-NOx

Senecionine Seneciphylline-NOx Senecivernine-NOx

Retrorsine Senkirkine

Intermedine-N-Oxide / Indicine-N-Oxide Heliotrine Europin

Intermedine Senecivernine

Echimidine-NOx

Lycopsamin-NOx Jacobine-NOx

Retrorsine-NOx Retrorsine Jacobine

Senecionine-NOx

More different PAs in herbal infusions.

Overview about PAs found at least 10% in positive findings in 2018.

Tea

Herbal infusions


PAs in herbal infusions and tea


No Monitoring data. Different effects: certain critical origins.

0

100

200

300

400

500

600

700

800

900

1000

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

50000

2015 2016 2017 2018

conc

entr

atio

n av

erag

e va

lues

conc

entr

atio

n m

ax v

alue

s

Sum of Pyrrolizidine alkaloids

Maximum value (HI)

Maximum value (tea)

Average values (HI)

Average values (tea)

PAs in herbal infusions and tea

High findings in 2017 strongly connected to Retrosine-NOx.


0

100

200

300

400

500

600

2015 2016 2017 2018

conc

entr

atio

n

Average values (herbal infusions)

Retrorsine-NOx

Seneciphylline-NOx

Senecionine-NOx

Retrorsine

Senecionine

Heliotrine-NOx

0200400600800

1000120014001600

2015 2016 2017 2018

conc

entr

atio

n

Average values (tea) Retrorsine-NOx

Senecionine-NOx

Retrorsine

sum of indicine + lycopsamine

sum of indicine-NOx +intermedine-NOx

Composition of PAs depending on analysed products.

Tropane alkaloids (TAs) in the spotlight

TA are secondary metabolic products formed to protect against herbivores by a great many of plant species

Well known plants are thorn apple (Datura stramonium), deadly nightshade (Atropa belladonna), henbane (Hyoscyamus niger)

More than 200 Substanzen are known; TAs investigated in detail are atropine ((-)- and (+)-hyoscyamine), scopolamine and cocaine

Toxikology: BfR-Statement 035/2014 and EFSA Statement 2013 Group ARfD of 0.016 µg/kg might be exceeded

by toddlers consuming cereals and cereal based products.


Structures Tropane alkaloids (TAs)

51

Scopolamin (Hyoscin)

Atropine, R- and S- (Hyoscyamin)

Tropin

Further: Littorine,

Norscopolamine, Homatropine,

etc.


https://de.wikipedia.org/wiki/Datei:L-Scopolamin.svg

https://de.wikipedia.org/wiki/Datei:Atropine_Enantiomers_Structural_Formulae_V.2.svg

Findings TA tea@ Eurofins

• Total number of tests: >1800 (since Jan 2015)

• Results from zero to > 9000 µg/kg in plant extracts

• In tea up to 15 µg/kg (Atropin) • max findings in herbal infusion/raw

material 2018

53

Atropine 9230 µg/kg

Scopolamine 4360 µg/kg

Atropine-NOx 31,8 µg/kg

Anisodamine 290 µg/kg

Norscopolamine 46 µg/kg


Contaminants in tea/herbal infusions

• contaminants are not caused by intended use of chemicals

• source can not determinated by analysis

• contamination can be reduced if source is known, but sometimes

there are multiple sources for the same contaminant

• is not always avoidable (especially from soil, air or water)

• sometimes specific for certain origins

• there are always some more…


55

Thank you very much!

Contact Johannes Jaschik: Fon: +49-(0)40-881 448-452 Fax: +49-(0)40-881 448-103 [email protected] www.eurofins.de

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