Contamination of Teas and Herbal Infusions – a Current Review of Findings for Pyrrolizidine Alkaloids and Further Contaminants
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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 www.eurofins.de Contaminants ABC Anthraquinone Nicotine Biphenyl, Bromide Ortho-Phenylphenol (2-Phenylphenol) Chlorate, Copper Pyrrolizidine alkaloids, Perchlorate, PAHs … Diethyltoluamid (DEET) QACs… Ethoxyquin Rare earth elements Folpet, Fluoride Smoke, S421 G… Trimethylsulfonium, Tallow amines Hexachlorobenzene U… I… V… J… W… K… X… Lead Y… Mercury Z… Johannes Jaschik, COTECA 2018 2 Residues vs. Contaminants Residues: Contamination: Whatever remains after the Presence of an unwanted use of use or application of a chemical which not originate of certain chemical an use in the material. from analytical perspective there is no difference A residue may act as a contaminant in material or environment it was not intented to be used in. Johannes Jaschik, COTECA 2018 3 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 Johannes Jaschik, COTECA 2018 4 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. Johannes Jaschik, COTECA 2018 5 Examples for Categories Mineral oils Photo initiators Heavy metals (MOSH/MOAH) (illegal) dyes Dioxins Radioactivity Allergenes Plasticizers Desinfectans Pesticides PAHs (e.g. QACs) GMO Irradiation Chlorate, Microbiology Perchlorate, Phosphoric acid, etc. Vet drugs … Fluoride … and other products in your portfolio Johannes Jaschik, COTECA 2018 6 Offer with different methods sample tea There is no „C.S.I. – analysis“ but quite a lot of specific work! all contaminants known What Eurofins can offer: group specific Specific methods Multi methods e.g. heavy metals e.g. mycotoxins Method Multi pesticides Method many different methods, Specific methods vet drugs modern equipment, e.g. microbiology experience in evaluation Johannes Jaschik, COTECA 2018 7 Keeping your risk low Not to analyse everything but to control for your risks and specific checking these. In order to have time and opportunity to… Enjoy your product ! Johannes Jaschik, COTECA 2018 8 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 Johannes Jaschik, COTECA 2018 9 Contamination of Lapsang Phthalimid Anthraquinone Biphenyl Cypermethrin Anthrachinon 2-Phenylphenol Bifenthrin Phthalimid (PI) Imidacloprid Bifenthrin Chlorfenapyr different ranking but Cypermethrin Thiamethoxam more important also Thiamethoxam Acetamiprid different concentrations Cyhalothrin, lambda- Cyhalothrin, lambda- Acetamiprid Thiacloprid Thiacloprid Carbendazim Glyphosate ranking for ranking for all teas Lapsang Johannes Jaschik, COTECA 2018 10 Lapsang contaminants Teas except Lapsang Lapsang 90,0 90,0 80,0 80,0 70,0 70,0 60,0 60,0 50,0 50,0 Anthrachinon 40,0 40,0 2-Phenylphenol 30,0 30,0 Phthalimid (PI) 20,0 20,0 Biphenyl 10,0 10,0 0,0 0,0 • 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 Johannes Jaschik, COTECA 2018 11 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 Johannes Jaschik, COTECA 2018 12 Biphenyl (2/2) Biphenyl: overview distribution 70,0 60,0 50,0 Evaluation for organic 40,0 conventional products takes into account 30,0 organic the different contamination 20,0 sources of Biphenyl. 10,0 But if the MRL is exceeded – 0,0 there is no further tolerance. <=0,01<=0,02<=0,05 <=0,1 <=0,2 <=0,5 >0,5 Graph for conventional and organic products comparable – contamination probable. Higher concentrations in mate and nutmeg. Johannes Jaschik, COTECA 2018 13 Anthraquinone (1/3) pesticide Detection in foodstuff with GC-MS/MS using multi method possible. Johannes Jaschik, COTECA 2018 14 Anthraquinone (2/3) Products: Products MRLs* Tea 0.02 herbal infusions 0.02 Packaging / inks Mate 0.02 packaging material Inks Herbs 0.01 Spices 0.02 dried fruits/vegetables 0.01 Anthraquinone: overview distribution *without concentration factor 60,0 50,0 Graph for conventional and 40,0 30,0 Conventional Organic organic products 20,0 comparable – 10,0 0,0 contamination probable. <=0,01 <=0,02 <=0,05 <=0,1 >0,1 Johannes Jaschik, COTECA 2018 15 Anthraquinone – source (3/3) Smoke Johannes Jaschik, COTECA 2018 16 2-Phenylphenol (1/2) Detection in foodstuff with GC-MS 2-Phenolphenol: overview using multi method possible. distribution 35,0 30,0 25,0 20,0 conventional 15,0 organic More than one effect. 10,0 5,0 0,0 <=0,01<=0,02<=0,05 <=0,1 <=0,2 <=0,5 >0,5 Johannes Jaschik, COTECA 2018 17 2-Phenylphenol (2/2) 2-Phenylphenol: overview (without citrus) 50,0 Products MRLs 45,0 Citrus /oil 5 40,0 Coffee 0,1 35,0 30,0 Fruits 0,05 25,0 conventional Herbal infusions 0,1 20,0 organic 15,0 Ink / packaging 10,0 Spices 0,1 5,0 Tea 0,1 0,0 <=0,01<=0,02<=0,05 <=0,1 <=0,2 <=0,5 >0,5 Now the graph shows the typical curve for contamination Contamination source Either use, as in citrus fruits, or Approved use contamination from packaging/ink or environment (smoke). Johannes Jaschik, COTECA 2018 18 Folpet/Phthalimide Phthalimide Molar Mass: 147,13 g/mol Phthalimide residues have Folpet to be multiplied by 2 in order to gain the Folpet residue. Regulation (EC) No 396/2005 as it stood before being amended by this Regulation shall continue to apply to Molar Mass: 296,56 g/mol products which were produced before 26 August 2016. Johannes Jaschik, COTECA 2018 19 Folpet/Phthalimide Relana/BNN forming under heating conditions 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. Johannes Jaschik, COTECA 2018 20 Folpet/Phthalimide data review Phthalimide: overview distribution Although some use of Folpet 45,0 (or Captan which contains 40,0 35,0 Folpet additionally) is known, 30,0 25,0 conventional contamination is the 20,0 prevalent factor of 15,0 organic 10,0 Phthalimide findings. 5,0 0,0 <=0,01<=0,02<=0,05 <=0,1 <=0,2 <=0,5 >0,5 Products MRLs If Folpet is actively used you can expect Tea 0,1 Phthalimide in neighbouring fields. Spices 0,1 Apple 0,03 Analysis possible with GC/MS(/MS) using multi Dried Chillies 0,03 methods for pesticides but use of isotope Herbal infusions 0,1 marked standards for Folpet and Phthalimide other fruits/concentrates 0,03 - 6 necessary. Johannes Jaschik, COTECA 2018 21 Heavy metals “…and some green tea leaves, particularly those from China, are contaminated with lead…” https://well.blogs.nytimes.com/2013/05/23/whats-in-your-green-tea/ 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. https://www.researchgate.net/publication/295858621_Metals_Contents_in_Black_Tea_and_Evaluation_of_Potential_Human_Health_Risks_to_Consumers Typically detected by single element analysis with AAS or ICP/MS. Johannes Jaschik, COTECA 2018 22 Lead Lead 40,0 35,0 30,0 25,0 20,0 conventional 15,0 organic 10,0 5,0 0,0 tea tobacco packaging material herbal infusions Only few data for organic available. spices No MRLs for tea and herbal infusions in general, evaluation is only possible for selected commodoties according to regulation 1881/2006 . Johannes Jaschik, COTECA 2018 23 Copper (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. Typically detected by single element analysis with AAS or ICP/MS. Products MRLs Cocoa 50 Coffee 50 Herbal infusions 100 Herbs 20 Oilseeds 30-40 Products with copper Spices 40 Tea 40 concentrations exceeding 10mg/kg Tobacco Johannes Jaschik, COTECA 2018 24 Copper (2/2) Copper: overview distribution 70,0 Contamination? Use? 60,0 Depending on the product. 50,0 40,0 Use of copper is allowed in 30,0 conventional organic organic farming. 20,0 10,0 0,0 <=0,1 <=0,5 <=2 <=10 <=20 <=40 >40 Evaluation is done accordingly to EU regulation 396/2005. Johannes Jaschik, COTECA 2018 25 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. Typically detected by single element analysis with AAS or ICP/MS. Produkte MRLs Tea 0,02 Shrimps 0,5 Herbs 0,01* Herbal infusions 0,02 Bigger topic in seafood! Spices 0,02 Mushrooms 0,01 Tobacco Johannes Jaschik, COTECA 2018 26 Mercury (2/2) Mercury: overview distribution 60,0 50,0 40,0 Not surprisingly the 30,0 conventional graph shows a sign for 20,0 organic contamination.