contamination of teas and herbal infusions – a current ...contamination of teas and herbal...
TRANSCRIPT
www.eurofins.de
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
3 Johannes Jaschik, COTECA 2018
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
4 Johannes Jaschik, COTECA 2018
Analytical options
How do you approach the assessment of contamination in tea and herbal infusion:
Looking at your product…
5 Johannes Jaschik, COTECA 2018
There are as many different substances which act as contaminants as products available.
Examples for Categories
Photo initiators
6 Johannes Jaschik, COTECA 2018
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!
7 Johannes Jaschik, COTECA 2018
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
8 Johannes Jaschik, COTECA 2018
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
9 Johannes Jaschik, COTECA 2018
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
Contamination of Lapsang
10 Johannes Jaschik, COTECA 2018
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
11 Johannes Jaschik, COTECA 2018
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.
12 Johannes Jaschik, COTECA 2018
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)
13 Johannes Jaschik, COTECA 2018
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)
14 Johannes Jaschik, COTECA 2018
Detection in foodstuff with GC-MS/MS using multi
method possible.
pesticide
Anthraquinone (2/3)
Products:
15 Johannes Jaschik, COTECA 2018
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)
16 Johannes Jaschik, COTECA 2018
Smoke
2-Phenylphenol (1/2)
17 Johannes Jaschik, COTECA 2018
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
18 Johannes Jaschik, COTECA 2018
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.
20 Johannes Jaschik, COTECA 2018
forming under heating conditions
Folpet/Phthalimide data review
21 Johannes Jaschik, COTECA 2018
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.
22 Johannes Jaschik, COTECA 2018
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
23 Johannes Jaschik, COTECA 2018
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)
24 Johannes Jaschik, COTECA 2018
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
Typically detected by single element analysis with AAS or ICP/MS.
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.
25 Johannes Jaschik, COTECA 2018
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.
26 Johannes Jaschik, COTECA 2018
Produkte MRLs Tea 0,02 Shrimps 0,5 Herbs 0,01* Herbal infusions 0,02 Spices 0,02 Mushrooms 0,01 Tobacco
Typically detected by single element analysis with AAS or ICP/MS.
Bigger topic in seafood!
Not surprisingly the graph shows a sign for contamination.
27 Johannes Jaschik, COTECA 2018
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
28 Johannes Jaschik, COTECA 2018
EPRW 2016
EFSA 2015
BfR 2018
Chlorate (1/3)
29 Johannes Jaschik, COTECA 2018
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)
30 Johannes Jaschik, COTECA 2018
This would lead to serious problems with a wide range of foodstuff.
Chlorate (3/3)
31 Johannes Jaschik, COTECA 2018
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.
32 Johannes Jaschik, COTECA 2018
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.
33 Johannes Jaschik, COTECA 2018
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.
34 Johannes Jaschik, COTECA 2018
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
????
35 Johannes Jaschik, COTECA 2018
Structures Pyrrolizidine alkaloids (PAs)
36
Retronicine
Senecionine Type
Lycopsamine Type Monocrotaline Type
Lycopsamine, Intermedine, Echimidine,
Lasiocarpine etc.
Senecionine, Senkirkin, Retrorsine,
etc.
Monocrotalin, Jacobine,
Trichodesmine
Johannes Jaschik, COTECA 2018
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)
Johannes Jaschik, COTECA 2018
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
38 Johannes Jaschik, COTECA 2018
Analytical view on PA
39
Retrorsine: negative in black tea
Seneciphylline N-oxide: added in black tea
Johannes Jaschik, COTECA 2018
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
Johannes Jaschik, COTECA 2018
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
Johannes Jaschik, COTECA 2018
PAs in herbal infusions and tea
42 Johannes Jaschik, COTECA 2018
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.
43 Johannes Jaschik, COTECA 2018
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.
50 Johannes Jaschik, COTECA 2018
Structures Tropane alkaloids (TAs)
51
Scopolamin (Hyoscin)
Atropine, R- and S- (Hyoscyamin)
Tropin
Further: Littorine,
Norscopolamine, Homatropine,
etc.
Johannes Jaschik, COTECA 2018
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
Johannes Jaschik, COTECA 2018
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…
54 Johannes Jaschik, COTECA 2018
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
?
Johannes Jaschik, COTECA 2018