Migration from coffee filter papers Presentation of Diploma

Migration from coffee filter papers Presentation of Diploma Thesis Matthias Fellner 18. 06. 2010

Who drank coffee today? • Should you worry?

Goals • Characterize commercial available Austrian coffee filter papers • Determine the migration of certain substances into coffee by simulating with water or organic solvents • Compare the results with safety limits and get a conclusion if the results call for further inquiry

Samples • 1 Melitta Original bleached! 2 Spar Kaffeefilter (Spar) • 3 Hofer Kaffee (Hofer) 4 Clever Kaffee-Filter (Billa) • 5 Brigitta Kaffeefilter (Zielpunkt) 6 Schlecker AS Kaffeefilter (Schlecker) • 7 Aromata Structured Coffee Filter Papers (Lidl)

Standards • ISO: International Organization for Standardization • CEN: Comité Européen de Normalisation • DIN: Deutsches Institut für Normung • ÖNORM: Austrian Standards Institute (formerly Österreichisches Normungsinstitut) • TAPPI: Technical Association of the Pulp and Paper Industry • SCAN: Scandinavian Pulp, Paper & Board Testing Committee

Used Standard Methods (compendium) • • DIN DIN EN 645 Preparation of a cold water extract EN 647 Preparation of a hot water extract EN 920 Determination of dry matter content EN 20287 Determination of moisture content 53124 Determination of p. H aqueous extracts EN 1541 Determination of formaldehyde 54603 Determination of glyoxal content

Cold and Hot Water Extraction • Simulating coffee with water • Cold water extraction (cwe): 10 g paper with 200 ml water for 24 h at room temperature (23°C) • Hot water extraction (hwe): 10 g paper with 200 ml water for 2 h at 80°C

A coffee filter paper (Size 4) • • • cost: ~1 -2 cents per filter weight: ~1, 60 - 1, 85 g contact area: 2, 875 dm² moisture content: 0, 2 - 1, 2% dry matter cwe: 1 bleached: ~5000 mg/kg 2 -7 unbleached: ~1500 -2300 mg/kg • dry matter hwe: 1 bleached: ~2700 mg/kg 2 -7 unbleached: ~800 -2400 mg/kg • p. H cwe: ~7, 2 -7, 5 (blank 6, 9) • p. H hwe: ~7, 0 -7, 4 (blank 6, 7)

Potassium permanganate method Titrimetric determination of volatile and none volatile organic substances in an extract 1 Melitta, 2 Spar, 3 Hofer, 4 Billa, 5 Zielpunkt, 6 Schlecker, 7 Lidl

Glyoxal • Used for paper coatings or cellulose derivatives • Photometric measurement (405 nm) of the product of HMBT + Glyoxal • Safety limit: 1, 5 mg/dm² -> all samples lower than that by a factor of ~1500 -2500

Glyoxal • Test close to detection limit • Comparison extraction with 100 ml to 200 ml with sample Nr. 6 - good result: – Absorbance nearly doubled – which means concentration is nearly the same

Formaldehyde • Main source paper coatings (problem in 1960 s), monomer from Urea-Formaldehyde resins • Photometric measurement (410 nm) of the product of Formaldehyde + Acetylacetone • Safety limit: 1, 0 mg/dm² -> all samples lower than that by a factor of ~200 -300

Pentachlorphenol (PCP) PCP has been used as a herbicide, insecticide, fungicide, algaecide, disinfectant -> preserving wood Very toxic: forbidden since 1989 Safety limit: 2 mg/kg Old method: Photometric test with 4 -amino -antipyrin showed no reproducible results -> gas chromatography necessary to confirm

Fraunhofer Institute for Process Engineering and Packaging IVV Freising - Germany

Scanning Electron Microscope Bleached Filter (Nr. 1) 1 mm Unbleached Filter (Nr. 4) 1 mm Bleached Filter (Nr. 1) 80μm Unbleached Filter (Nr. 4) 80μm

Headspace Gas Chromatography Mass Spectrometry • • • Sample in 15 ml Vial + 150°C + 1 bar Gasphase analyzed with GC-MS Identification with library and standards Quantification tricky Results: All filters seam to be clean, except some small peaks which could not be identified

Headspace GC-MS Examples Filter 1 gas chromatogram: except airpeak (3, 98) no big peaks Same chromatogram: the small peaks couldn’t be identified with the library Filter Package 1: more bigger peaks, some could be identified with the library and with measurement of standards 17, 37 = benzaldehyde; 21, 44 acetophenone -> printer’s ink?

X-ray fluorescence spectroscopy Results: • Filter Papers: Sometimes detectable concentrations of Na, S, Cl and Ca but always under 0, 3% -> questionable (contaminations from hands possible and too light elements) • Filter Packages: Same but: – – Fe, Cu, Sr 0, 01 -0, 1% Al 1 -4% printer’s ink? Si 1 -5% Ca 8 -24% - Ca. CO 3 filler material

Multimethod Extraction with Accelerated Solvent Extraction (ASE) GC-MS (Shimadzu QP-5000) Determination of: • Benzophenone • Diisopropylnaphthalene (DIPN) • Michler's ketone • Phthalates • Pentachlorphenol (PCP)

ASE + Sample Preparation • Preextraction with empty cartridge • Dichloromethane extraction -> 3 times for 15 minutes at 100 bar and 80°C • Direct GC-MS analysis with standards • Only PCP needs derivatization

Results Phthalates Nothing found at: Dimethylphthalat, Diallylphthalat, Dipropylphthalat , Benzylbutylphthalat, Dicyclohexylphthalat, Diphenylphthalat, Didecylphthalat, Diisooctylphthalate, Diisodecylphthalat, Dioctylphthalate

Echelle Plasma Emissions GC Detector EPED • P/T (Purge-and-Trap) sampling system • EPED: GC Detector for sulfur and halogens chlorine, bromine, fluor, iodine – Atomization of molecules at 8000 K and atmospheric pressure in a Helium plasma – Detection of emission lines with a polychromator

Other results Multimethod and EPED • The lab work at both methods is done and the measuring is finished • But the reprocessing of the data is not finalized to be presented • So far nothing indicates any high concentrations of any concerning substances

Conclusion • No safety limits are exceeded at Formaldehyde, Glyoxal (PCP pending) • Concentrations of Phthalates low, but concerning • No indication of toxic metals (Hg, Cd, Pb, Chrom VI) • No indication of migration from the packages • No indication that recycled paper was used • Some results still open but so far nothing to really worry

Thanks to Research Division Food Chemistry • Ingrid Steiner • Kathrin Scharnhorst • Herbert Hafner Product Safety and Analytics • Ludwig Gruber • Gerd Wolz • Nicole Weise • Dominik Fiedler • Michael Barwitz

Thank you for your Attention