Shimadzu Lunch Seminar
"From Water to Wine" - analytical tools for determination of
contaminants in food and environmental samples using atomic
spectroscopy
Pau, 04.02.2019
Uwe OppermannShimadzu Europa GmbH, Duisburg
ICPMS the high sensitivity add-on to your analytical toolbox:
Determination of contaminants in food and food packaging
Uwe OppermannShimadzu Europa GmbH, Duisburg
Food Market Place Europe
⚫ Market Size 1109 bn € ( )
⚫ Biggest industry segment in EU (15.2%)
⚫ 294000 Companies
⚫ R & D Invest 2.9 bn € ( )
Data & Trends of the European Food Industry Oct. 2018, Copyright: FoodDrink Europe, Brussels
„Top 10“ in Europe/ World
Alcoholic Beverages in Europe (TO)
https://de.statista.com/outlook/10000000/102/alkoholische-getraenke/europa#market-revenue
The „Alcohol Belts“ in Europe
https://en.wikipedia.org/wiki/Alcohol_belts_of_Europe
Quality Control
Is our food safe ????
⚫ Nobody can answer this question …….
⚫ ….. but It has never been ckecked better than today
⚫ EFSA: More than 97% of food in the EU contains Pesticide residues with the tolerance limits: https://www.efsa.europa.eu/en/press/news/150312
⚫ 97.4% below the max. allowable concentration
⚫ 1.5% above the allowable concentration
⚫ EFSA (2016): 27 of 28 EU-Memberstates reported 710.000 samples
⚫ The failure rate for Metal Contaminants was higher than in other classes (> 5%)
https://efsa.onlinelibrary.wiley.com/doi/epdf/10.2903/sp.efsa.2018.EN-1358
Results after Determination
Published results of LGL in Bavaria:
⚫ Fruit spirits
⚫ Number of samples: 159
⚫ Claims: 77 (48,4 %)
⚫ Reason of claim:
⚫ Wrong declaration
⚫ High concentration of Ethyl acetate, Propanol-1, Butanol-2
⚫ Particles from Filter material Asbestos, Glas und Chrysotil fibres
⚫ Metal contaminants such as copper
https://www.lgl.bayern.de/lebensmittel/warengruppen/wc_37_spirituosen/index.htm
Properties to determine:
• Composition
• Essential Elements
• Toxic Elements
• Taste, Color.....
• Contaminants
Food Quality…….
Laws and Regulations:
• Drinking Water Regulation
• Beer Purity Law
• Foodstuff and commodity Act
• European Food Law
• European Food Safety Authority
More Regulations…..
⚫ Regulation (EU) 1881/2006 setting maximum levels for certain contaminants in foodstuffs
⚫ European Wine Regulation from 9. May 2012
⚫ Mineral- and Tablewater- Regulation 1. August 1984 (BGBl. I S. 1036) witharticle 25 from 5. July 2017
⚫ etc…..
One Stop Vendor in Food Analysis
A
Z
AAS
ICP-OES/MS
LCMS
TOC
FTIR
GCMS
UV
TM
LC
GC
Selecting the Method
⚫ Selection of the best Method:
⚫ Element/-number
⚫ Concentration: major-, minor- or
trace elements
⚫ Sample preparation
⚫ Shimadzu Instruments:
⚫ RFA (EDX)
⚫ AAS (Flame/Furnace)
⚫ ICP-OES
⚫ ICP-MS
Se
ns
itiv
ity
0.000001
0.0005
0.005
0.05
0.5
50 Comparison of Detection limits
RFA
(mg/l)
ICP-
OES
Gra
ph
ite F
. -AA
S Fla
me
-
AA
S
ICPMS
12U. Oppermann/ K. Kartaschew | ICPMS | Food user meeting Bruxelles
Methods
⚫ Beer Analysis⚫ MEBAK/EBC Methods for Cu, Mg, Al, Zn with AAS
⚫ MEBAK Method for Multi- Element Analysis with ICP-OES/MS
⚫ Water Analysis ⚫ DIN 38406- 6/-7/-8 Determination of Pb, Cu, Zn with AAS
⚫ DIN 38406-22 Determination of 22 Elements using ICP-OES
⚫ DIN EN ISO Determination of selected Elements using ICP-MS
⚫ Wine Analysis⚫ OIV-MA-AS323—07 Multi- Element Analysis with ICP-MS
World Wine Production
MillionHektar
MillionHektoliter
Hektoliterpro Hektar
World 8 260 33
Europe 5 200 42
Asia 1.35 6
America 0.75 47 62
Africa 0.31 10
Ozeania 0.10 6
Germany 0.11 9 81
Croatia 0.03 1.4 46
European Wine Regulation
Control Limits:
Aluminium8.00 mg/l
Arsenic 0.10 mg/l
Lead 0.25 mg/l
Boron 80 mg/l
Cadmium 0.01 mg/l
Copper 2.00 mg/l
Zinc 5.00 mg/l
Tin 1.00 mg/l
Trichloromethane 0.10 mg/l
Trichloroethene 0.10 mg/l
Tetrachloroethene 0.10 mg/l
Trichloromethane, Trichloroethene & Tetrachlorethene (total) 0.20 mg/l
Copper/ Zinc
Concentration
• Metallic bitter taste > 1.0 mg/L
• Generate turbidity > 0.5 mg/L
• Copper oxidation > 0.5 mg/L
• Reducing the flavour >0.5 mg/L
• Influence on fermentation > 20 mg/L
Table 1: Influence of copper concentrations in wine
Antimony?
Wine in PET- Bottles – Prof. Dr. Rainer Jung, University Rhein/Main
Languedoc Producer SKALLI in 2010: 2,5 Mio. PET bottles
http://blog.campus-geisenheim.de/index.php/2010/12/wein-aus-pet-flaschen-und-bechern-prof-dr-rainer-jung-im-interview-mit-dem-wiesbadener-kurier/
Quantitative Analysis of Metals by AAS
Sequential in Flame- and Graphite furnace -Atomisation with AA-7000:Determination of Cu and Zn
http://www.shimadzu.eu/sites/default/files/Application_wine_SCA_120_026.pdf
Sample Preparation
• Dilute with H2O 1:1• Alcohol Concentration ca. 5 %• HNO3 Concentration 0.1 %• Calibration Range: 0.005 to 50 mg/L.
Quantitative Analyse of Metals
…using simultaneous ICP-OES: ICPE-9820
http://www.shimadzu.eu/sites/default/files/AN_SCA_115_023_Wine_0.pdf
Quantitative Analysis of Metals
….with high sensitivity ICPMS-2030
http://www.shimadzu.eu/sites/default/files/AN_SCA_115_023_Wine_0.pdf
ICP Coupled with Mass Spectrometry
Mini Torch
TechnologyMass Detector
Detection, Identification
and Quantitation of
Ionen
⚫ Analysis Technique: ⚫ Multi-Element Analysis : simultaneous as in ICP-OES⚫ Extreme Sensitivity => Analysis in Ultra- trace range (< ppb => ppt).
Multielement Analysis in Wine
Table 1: ICPMS-2030 Results of Wine Sample [µg/L]
Table 2: Recovery rates
Packaging: PET Bottles
⚫ Contamination by Sb2O3
⚫ Sb2O3 as Catalyst during PET Production
⚫ Start concentration Sb in PET bottle: 1,65 µg/l
⚫ EU limit exceeded after 30 days > 5 µg/l
⚫ At 40C after 4 days10 µg/l
Determination of Sb in alcoholic beverages, Schmitz, A. et al., Niederrhein University of applied Sciences, Krefeld, 2012
Packaging: Glasbottles
⚫ Transmission/ Reflection of Glas
⚫ Sun protective glas with Fe (II)/ (III), Cu (II) oxide
⚫ UV-2600 with ISR-2600plus
Chromium in Foodpackaging (1/2)
⚫ EU Packaging Directive 2014 (VerpackV)⚫ Limit values for Pb, Cd, Hg and Cr VI < 100 mg/kg
⚫ Speciation analysis using LC-ICPMS⚫ Toxicity of trace elements depends on concentration and oxidation state
⚫ Differentiation of Cr(III) and Cr(VI)
⚫ Cr(III) is not critical, Cr(VI) is toxic
⚫ Systemconfiguration⚫ ICPMS-2030
⚫ Prominence inert HPLC
Chromium in Foodpackaging (2/2)
⚫ EU Packaging Directive 2014 (VerpackV)⚫ Limit values for Pb, Cd, Hg and Cr VI < 100 mg/kg
⚫ Calibration Curves⚫ Chrom III: 50, 100, 200, 500, 1000 ng/L
⚫ Chrom VI: 5, 10, 20, 50, 100 ng/L
⚫ Chromatograms of LC-ICPMS⚫ Overlay of Concentrations
⚫ Clear differentiation of Cr III & Cr VI
Physical Testing
⚫ Bottle cork⚫ Wine- and Champaign bottles
⚫ Whisky bottles
⚫ Measurement⚫ Torque
⚫ Extraction force
⚫ ISO 9727-5:2007
⚫ Bottle sizes from 250 ml to 750 ml
Sensoric Testing
⚫ Flavor/ Off flavor⚫ Natural flavor (exclusively from the fruit)
⚫ Synthetic flavors (not legal in fruit destillates)
⚫ Sensoric Quality control⚫ Color/ appearance
⚫ Smell
⚫ Taste
⚫ Testcriteria for Fruit Spirits
http://www.dlg-verbraucher.info/de/testergebnisse/spirituosen/regionales-im-trend-obstgeiste-und-braende.html
Sensoric Testing
1: Color and appearence
2: Smell
3: Taste
Prof. Erich Leitner, Institute of Analytical Chemistry and Food Chemistry
⚫ One of the best detectors: the human nose
Olfactometry for GCMS
Aroma Analysis
Substance Aroma Impression Threshold value [mg/L]
Ethanol alcoholic 100
Vanillin Vanilla 0.02
Hexanal fresh Gras 0.0045
Methylthiole rotten/ sour 0.00002
2,4,6-Tribromoanisol musty/ mouldy 0.00000002
20 pg/L (!!!)
Prof. Erich Leitner, Institute of Analytical Chemistry and Food Chemistry
⚫ Enhanced selectivity: Triple-quadrupole technology
Aroma Analysis using GCMSMS
13.0 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 14.0
0.25
0.50
0.75
1.00
1.25
(x100,000)
2:210>195 TCA
1:215>197 TCA d5
13.0 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9
0.25
0.50
0.75
1.00
1.25
1.50(x100,000)
2:210 TCA
1:215 TCA d5
Prof. Erich Leitner, Institute of Analytical Chemistry and Food Chemistry, TU Graz
GCMS-QP2020 GCMS-TQ8040
Apple Spirit 1
Prof. Erich Leitner, Institute of Analytical Chemistry and Food Chemistry, TU Graz
Apple Spirit 1 (Zoom)
Apple Spirit “Zoom”
1: Octan acid 4: 2-Methylbutyrate2: Terpineol 5: 1-Decanol3: Citronellol 6: Decane acid
Prof. Erich Leitner, Institute of Analytical Chemistry and Food Chemistry
Conclusion
Shimadzu offers the full Productportfolio
and „taylor made“ solutions in
Quality control of Food and food packagings
for the highest level of food safety
Questions/ noch Fragen/ avez-vous des questions?
Thank You!
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