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!