Identification of Adulteration or origins of whisky and ...

Identification of Adulteration or origins of whisky and alcohol with

the Electronic Nose

Dr Vincent Schmitt,Alpha M.O.S [email protected]

Alpha M.O.S.Eastern Analytical Symposium, November2004

Alcoholic beverage challenges

Taste and smell in the beverage industry are important for the success of the product.

Aroma and taste reflect the quality point of view, for example:- the vineyard- the type of distillation- the age- the contamination- the packaging

Taste and odor analysis are currently carried out by sensory panels. Actually, it is extremely problematic for production control. It is also very difficult to screen a large number of samples in one shot.

Alcoholic beverage challenges

Needs of Industry

Control objectively and rapidly from raw materials to finished products

Monitor the Volatile Organic Compounds (VOC) quality of new production batches

Detect out of specification odor and taste products

Get a robust technique that correlates with human perception and provides fast answers

Human nose and Sensing systemsimulation

Recognized as BRAZILIAN

Comparison of the odorby pattern recognition

DataProcessingAcquisition

Raw signals Processed signal Data treatment

RESULTS

Brain NeuronsSmellOdor

RECOGNIZED ASBRAZILIAN

Electronic Noses

The advantages of this new technique:

� Volatile and odor measurement systems

� Both qualitative and quantitativeresults

� Solid, liquid or gaseous samples

� Correlation with human perception

� Fast(a few minutes per sample)

� Robust

� Very little sample preparation

αPROMETHEUS

A development platform combining 2 technologies:

• ααααFOX - Sensor array system

Flexible sampling system, up to 18 sensors, QC or laboratory tool

• ααααKronos - Fingerprint MS

High discrimination power, SCAN and SIM available, qualitative and quantitative

Fingerprint Mass Spectrometry (FMS) Principle

Multi organolepticsystem: principle of one analysis

Sampler forvolatile analysis

Fingerprint measurement

Multivariate analysis

Printingthe report

Crimping the sample in a vial and headspace generation

Raw data are transferred in a Library Prediction

Results

Fingerprint identification withchemometrics

Sampling Data Processing

Headspace

SPDE SPDE (PDMS/AC)(PDMS/AC)

Multivariate Statistics Tools

Data Processing

Discrimination Quantification Quality control

Application 1: Whisky Study

Aim: Cross polluted whisky discrimination. Detection of Orange, Mint, Pastis and Gin pollutions

Reference Description ofWhisky sample Characteristics

A1, A2, A3, A4 Accepted quality -

PO Polluted with orange Limonene (68 uma)Terpilonene (93 uma)

PM polluted with mint Menthone (112 uma)

PP polluted with pastisAnethole (148 uma)Estragole(149 uma)

PG polluted with gin α and β pinène (93 uma)

System configuration

• ααααKronos - Fingerprint Mass Spectrometry

New automated dynamic extraction technique

2,5mL HeadspaceSyringe

Internal coating

Steel needle

Conical tip withside port

56mm

Cross-sectionview

Specific syringe coating

• Solid Phase Dynamic Extraction (SPDE) Option

Analytical parameters

Sample preparationQuantity of sample in the vial 0.5ml whisky / 0.5ml waterTotal volume of the vial 10 ml

Headspace generationHeadspace generation time 15 minHeadspace generation temperature 70°C

SPDE extraction / injectionSPDE Syringe PDMS/AC syringeStroke Number 80 strokes / 2500µµµµl pumped / 500µµµµl/secAnalysis time 15 minPredesorption time delay 15 sec, 0.6 ml N2 injected / 50 µµµµL/sec

Application: results with the Fingerprint Mass Spectrometry

Anis polluted sample MSThe chemical compounds characteristic of Anis are clearly detected (anethole and estragole respectively mass 147 and 148).

SPDE SPDE (PDMS/AC)(PDMS/AC)

Anetholeestragole

Calculation type RSD (%)1 - 55 uma peak 1.72 - TIC average 3.0

In order to validate the analytical parameters the Residual Standard Deviation has been computed on one mass 55 and on the TIC (Total Ion Current). In this case, an excellent reproducibility is obtained.

Clear detection of Anis characteristic massesExcellent repeatability of the measurements

Application: Principal Component Analysis results

Acceptables

OrangePastis

Gin

Menthe

� A PCA model allows to represent the difference measured with the SPDE/MS system.

� The Accepted samples are grouped together and the samples with different defaults are spread around these reference samples.

Excellent distinction between the acceptable samples and the polluted samples

Application 2: Wine packaging selection

Aim: Study the shelf life of wine during eight months in two different packagings: Glass bottle (B) and Can (C).

Sample designation Alpha-MOSReference

Red wine in bottle – 1 month R_B_1_565Red wine in bottle – 2 month R_B_2_605Red wine in bottle – 3 month R_B_3_074Red wine in bottle – 4 month R_B_4_998Red wine in bottle – 5 month R_B_5_087Red wine in bottle – 6 month R_B_6_817Red wine in bottle – 7 month R_B_7_332Red wine in bottle – 8 month R_B_8_928Red wine in can – 1 month R_C_1_656Red wine in can – 2 month R_C_2_746Red wine in can – 3 month R_C_3_481Red wine in can – 4 month R_C_4_018Red wine in can – 5 month R_C_5_953Red wine in can – 6 month R_C_6_337Red wine in can – 8 month R_C_8_557

Analytical conditions

Sample preparationQuantity of product in vial 2 grVolume of the vial 10 ml

Head-space generation parametersGeneration time 5 min.Generation temperature 65 °C

Head-space injection parametersInjected volume 5000 µlInjection speed 150 µl/sSyringe temperature 70 °C

Acquisition parameters KRONOSMode ScanScan range 50-110Acquisition time 90 secondsAccuracy 25

System configuration: ααααKronos - Fingerprint Mass Spectrometry

Results

The First month is the reference.

At the beginning there is a big change in the quality of the wine compared to the reference month.

The wine in can ages slightly more rapidly than the wine in bottle.

After 5 months, the wine has changed but it reaches the same target whatever it is in Can or in Bottle.

0

0,5

1

1,5

2

2,5

1 2 3 4 5 6 7 8

Months

Dis

tan

ce Bottle

Can

The distances between the sample of month 1 and each other month have been reported on the following graph:

Reference

After 5 months, the wines in can or in bottle reach the same target quality.

Conclusion

The results obtained demonstrate the ability for the Kronos Mass Spectrometry E-nose to identify several origins, process, packaging effect and to detect counterfeits on the market.

Results show:Excellent discrimination between all the alcoholic

beverage qualities

Excellent repeatability of the measurements

Benefits of the method

�Fast, reliable and simple to use

�Objective identification of grade products

�Used for qualitative and quantitative analysis of complex odorous matrices

Raw material (rice,

malt) selection and Quality control

(Fox, Gemini)

Ageing control(Prometheus, Kronos,

Astree)

Qualitative and quantitative control of yeast (Fox)

Astringency determination

(Astree)

Control of barrel burning

Wood chip toasting

(Fox, Gemini)

Blending controlPackaging selection

Counterfeit and fraud

detection (Kronos, Astree)

Trade mark protection

Electronic Nose and Tongue Products

Research& Development2nd generationof hybrid system

αααα PROMETHEUS

R&D Quality Control

αααα FOX / αααα KRONOS

Factory Quality ControlProduct conformity test

αααα GEMINI

Research & DevelopmentElectronic tongue

αααα ASTREE

Please come and see us

Booth # 411

Website: www.alpha-mos.com

Identification of Adulteration or origins of whisky and ...

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