food provenance by elemental and isotopic fingerprint methods · food provenance by elemental and...

FOOD PROVENANCE BY ELEMENTAL AND ISOTOPIC

FINGERPRINT METHODS

Thomas PROHASKA

Johanna IRRGEHER, Andreas ZITEK, Tine OPPER Sylvie BONNET, Anastassiya TCHAIKOVSKY University of Natural Resources and Life Sciences Vienna, Department of Chemistry, Division of Analytical Chemistry, VIRIS-Laboratory for Analytical Ecogeochemistry Konrad-Lorenz-Straße 24, 3430 Tulln, Austria

BOKU University and Research Center - Tulln

Research focus: bioresources, renewable resources, biologically based technologies Construction: 2009 - 2011 Lab relocation: April-2011 Opening ceremonies: Sep-2011

Ecology

Analytical Chemistr

y

Geo-chemistry

Biology

anthropogenic factors

Ökosystem

natural factors

natural factors

anthropogenic factors

presence

Ökogeochemie

past

Analytische Chemie Analytical

Ecogeochemistry other

sciences

other sciences

Analytical Ecogeochemistry

Rationals

Thuna, made in Austria

Global food trade

authenticity adulateration ...how to control???

Rationals

Consumer protection:

Food safety

Genuineness (‚You get what you pay for‘)

Producer protection

Competition

Proof of provenance (consumer confidence)

Protection of regionality

Diverstiy of production

Specific production processes

Food Authenticity/Food Provenance

EU regulation

http://ec.europa.eu/agriculture/quality/

Traceability solutions

Traceability solutions

Traceability by

Software solution

Databases

www-information platforms

Marking by

RFID-tags

Code systems

Animal passports

Animal tattoos

....added systems are not fraud-resistent

Independent solutions

Information is an intrinsic food property and does not have to be added

Information is unique for the food commodity

Information can be identified (simple and cheap)

Information is fraud resistant

Analytical methods (1)

Molecular-biological methods

DNA (e.g. DNA marker in olive ois)

ELISA technique (cultivation of specific antibodies for the determination of defined proteins)

Amplified Fragment Length Polymorphism (AFLP) markers (fish, seafood)

Genetic fingerprint analysis (e.g. cereals)

Identification of specific chemical and physical parameter

(e.g. honey: water content, ash content, sugar content, pH, differential scanning calorimetry; rheology)

Sensory analysis (electronic nose)

(e.g. wine: colour, taste, aroma....)


Identification of specific components and evaluation using multivariate statistics

IR spectroscopy (e.g. fruits, wine, sugar addition to honey)

Raman spectroscopy (e.g. adulteration of oils)

Front Face Fluorescence Spectroscopy (measurements of fluorophores e.g. aromatic amino acids; vitamine A and B2, chlorophyll)

Chromatographic methods (HPLC; GC) (e.g. beta-lactoglobuline in milk, organic acids in fruit juices; adulteration of olive oil)

Organic mass spectrometry (non targeted fingerprint)


Identification of elemental and isotopic fingerprints

specific isotope ratios (isotopic fingerprints)

NMR; SNIF-NMR (H,C)

IR-MS (GSMS) (H,C,N,O,S)

TIMS (Sr,Pb)

ICP-MS (Sr,Pb,U,Ca,S,B)

Identification of specific elements and evaluation using multivariate statistics (multielement fingerprints)

AAS

ICP-AES

ICP-MS

elemental fingerprint

isotopic fingerprint

natural variation locally specific signal

<< intrinsic marking >>

Elemental and isotopic fingerprinting





(multi)- elemental

spikes

enriched stable

isotopes

marking via elemental spikes or enriched isotopes

<< extrinsic marking >>


Nuclide map

17

> 3000 nuclides

254 stable nuclides

34 primordial radionuclides

50 daugther nuclides of

primordial radionuclides

Elemental and isotopic fingerprint

18

Source: Husted et al. J. Anal. Atom. Spectrom. 2011, 26, 52-79

Elemental fingerprint of REE for proof of authenticity / origin

Determination of elemental fingerprints (e.g. rare earth elements)

1

10

100

La Ce Pr Nd Sm Eu Gd Dy Ho Er Yb Lu

certified values

literature values (Sen Gupta et al.)

MCN100 (MR)

MCN6000 (LR)

Natural variation of isotopic systems

Natural chemical processes

Radioactive decay (e.g. U, Pb)

Redox reactions (e.g. Fe)

Photoreactions (e.g. Hg)

pH dependent reactions (e.g. B)

Natural physical processes

Diffusion (e.g. C, H, O)

Precipitation (e.g. H, O)

Natural biochemical processes

Microbial activities (e.g. S, N)

Plant activities (e.g. C, Si) 21

18O

18

O

18O

Natural variation of isotopic systems

Isotopic Systems Used in Food Provenance Studies

The ‚big 7‘

agricultural

photosynthesis

food chain

emission

physiology

geography

environment

anthropogenic

biological

geology climate

rocks, soils precipitation

δ15N

δ13C

δ2H

δ18O δ87Sr

δ208Pb

δ34S

Pb Isotopic Variation

204Pb; 206Pb; 207Pb ; 208Pb Pb

Radioactive decay: 238U ---- 206Pb 235U ---- 207Pb 244Pu/232Th ---- 208Pb 204Pb – 200Hg

Sr Isotopic Variation

84Sr; 86Sr; 87Sr; 88Sr Sr

Radioactive decay: 87Rb ---- 87Sr

Strontium

Sr isotopic system

88Sr 82.58 %

84Sr 0.56 %

86Sr 9.86 %

87Sr 7.00 %

- ubiquitous

- chemical similarity to Ca

Strontium

Rubidium

Sr/Rb isotopic system

87Rb → 87Sr + β- + v + Q T1/2 … half life(T1/2 = 48.8*109 a) λ … decay constant(λ = 1.42*10-11 a-1)

85Rb 71.17 %

87Rb 27.83 %

88Sr 82.58 %

84Sr 0.56 %

86Sr 9.86 %

87Sr 7.00 %

variation of 87Sr/86Sr with geological provenance

• geochemical composition

• geological age

Sr ↔ Ca

Sr cycle

Food authentication

Provenancing

of strawberry raw products

using elemental and isotopic fingerprints

– a pilot study

Sample preparation

Cutting, freeze drying and homogenization

(replicate analysis n=5)

Microwave assisted acid digestion

Sr/matrix separation with a specific resin

(elimination of Rb interference)

Measurement of the elemental pattern

with ICP- Quadrupol MS ‘Nexion 300D’

1

2

3

4

Sample preparation

Concentration screening with

ICP-Quadrupol MS ‘Nexion 300D’

Data evaluation

Blank, Rb, Instrumental Isotopic fractionation

5

6

7

Measurement of the isotope ratio 87Sr/86Sr with

Multicollector-ICP-MS ’Nu Plasma HR’

f

86

87

meas

86

87

corr

86

87

m

m

Sr

Sr

Sr

Sr

Results – elemental pattern

-RM1

Results – Elemental Pattern

0.70200

0.70400

0.70600

0.70800

0.71000

0.71200

0.71400

87Sr

/86Sr

Sr isotopic data

Arg

en

tin

a

Ch

ina

Eg

yp

t

Mo

rocco

Po

lan

d

Tu

rkey

Mexic

o

Sr isotopic fingerprinting

Applicability of Sr isotope ratios

Regional signal can be determined via bioavailable fraction from soil

Direct link from soil to plant

Annual and seasonal stability

Parameters to be considered

Change of irrigation

Influence of fertilizer

Regional heterogeneity of the soil

Marchfeld asparagus

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1

0,7050

0,7060

0,7070

0,7080

0,7090

0,7100

0,7110

0,7120

0,7130

0,7140

0,7150

0,7160

0,7170

0,7180

0,7190

0,7200

0,7210

0.7210 0.7050

Marchfeld: Sr range and source

harvest 2005: n = 20

harvest 2006: n= 35

Soil sample

(7 locations)

Soil sample

(1 location)

Soil extracts

1M NH4NO3 • Sr range is stable on an annual basis

• Sr source: leachable Sr in soil

• Sr signal in extract different to total soil

87Sr/86Sr

Sr sources

Sr isotopic composition

Maternal rock

Wet and dry deposition

20 % weathering

80 % recycled Sr

Miller EK, Blum JD and Friedland AJ, Nature 362, 1993, 438-441

87S

r/86S

r

A s

oil

dig

A s

oil

ex

B a

spara

gus

B s

oil

dig

B s

oil

ex

D a

spara

gus

D s

oil

dig

D s

oil

ex

D a

spara

gus

E s

oil

dig

E s

oil

ex

E a

spara

gus

F s

oil

dig

F s

oil

ex

F a

spara

gus

87Sr/86Sr (U (k = 2))

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0.7045 0.7055 0.7065 0.7075 0.7085 0.7095 0.7105

Marchfeld: Sr range and source

Marchfeld

n = 55

Hungary

n = 18

Germany

n = 6

Netherlands

n = 10

Mainz

Traceability

• Marchfeld: hand picked by lab staff (traceable)

• other regions: purchased at the market (not traceable)

• include other signatures

• multivariate statistics

(87Sr/86S

r)

2.1140 2.090 2.110 2.130 2.150 2.170 2.190 2.210

0.859 0.869 0.879 0.889 0.899 0.909 0.919 0.929 0.939 207Pb/206Pb

208P

b/2

06P

b

Marchfeld

unknown. Hungary

Netherlands

Slovakia

Carinthia (AT) Styria (AT) Germany

Hungarian sample near Austrian border

...isotope ratios do not fillow political borders

Marchfeld

Marchfeld asparagus

3D main component analysis

Hungarian sample near

Austrian border

Marchfeld

d18O d15N

Pb208/206

Predicting Provenance

Complementary approaches for the verification of food provenance

Databases

Origin is determined by comparison to data wihtin a database

• Requires data from all provenances (authentic samples)

• Expensive (large number of datas)

• Stability has to be proven (regular update)

Isoscapes

Origin is detemrined by comparing the data within a food to interpolated geo-climatic factors depicted in an isotopic map

• Prediction of areas with no isotopic data

• Large scale data might overlook regionality

• Annual/seasonal stability has to be proven

δ18O in plants

(source: Simon Kelly)

Distribution of C3 and C4 plants

H and O isoscapes

www.waterisotopes.org

• Continuous maps of isotope ratios for authenticity,

migration and more

Assessment of ‚isoscapes‘

geology

87Sr/86Sr

• Isoscapes for

• Bioavailable 87Sr/86Sr in soils

• 87Sr/86Sr in rivers and lakes

Sr isoscapes

Sr – isoscape –

definition of a region by the bioavailable Sr

50

10 km

Sr – isoscape –

definition of a region by the bioavailable Sr

51

Sr isoscape work - VIRIS database

52

Isocape Austria: Database of 87Sr/86Sr

• Input via Excel spread sheets in

different categories of projects and

samples, including quality judgement,

instrumental settings, pictures, links to

original data, citation etc.

• Searching data possible • by a wide variety of requests, including

the measured parameter (e.g. 87Sr/86Sr) • by a geographical window that can be

opened from the database and that allows to select a geographical area

Sample type could be wood, water, fish hard parts, soil, …

VIRIS Database • Selected datasets can be provided and

shared via the Isoscape Austria Portal

• Searching for categories and

download possible

Sr isoscape work - Isoscape Austria Portal

TRACE project (trace.eu.org)

Combining areas of origin

δ2H

δ18O

δ34S

δ87Sr

intersection – area of provenance

Combination of isotopic and elemental information:

Determination of the origin of green coffee beans

🏃

Microwave digestion

Sr/matrix

separation

87Sr/86Sr Multielement

analysis

ICP-SFMS

Element 2

MC-ICP-SFMS

Nu Plasma HR

ICP-QMS

Elan DRCe

Standard protocol ICP-MS

Standard protocol IRMS

grinding

drying

δ13C

Elemental

analyser(EuroEA)

δ18O δ34S

δ15N

Isoprime

IRMS (Sira II; Isoprime)

δ2H

Continental origin

59

Afrika

Zentral

amerika

Asien

Süd

amerika

Canonical discriminant analysis

Multielement analysis

87Sr/86Sr

98.1 % classified

60

Regional origin (Rodrigues et al., European Food Research and Technology)

87Sr/86Sr

δ 18O

RWRW

ET

ETET

TZ

TZ

TZ

TZ

TZ

KE

KE

KE

KEKE

KEKEKE

KE

KE

KE

MW

MW

-5 -4 -3 -2 -1 0 1 2 3 4 5

PC 1: 47.67%

-4

-3

-2

-1

0

1

2

3

4

PC

2: 3

3.1

9%

RWRW

ET

ETET

TZ

TZ

TZ

TZ

TZ

KE

KE

KE

KEKE

KEKEKE

KE

KE

KE

MW

MW

Kenia

Tanzania

Malawi

Ruanda

Äthopien

61

Case study: Hawaii

• 87Sr/86Sr

• δ13C, δ15N, δ18O, δ34S

• Lanthanide, B, Na, Mg,

Al, Cr, Mn, Fe, Co, Ni,

Cu, Zn, Ga, Rb, Sr, Mo,

Ba, Pb and Bi

22°

21°

20°

19°

160° 159° 158° 157° 156° 155°

Kaui

Oahu

Molokai

Maui

Hawaii

Hawaii – origin of islands

62

• δ34S

• Lanthanide, B, Al, Fe, Ni, Cu,

Rb, Sr, Mo, Ba Hawaii

Kauai

Oahu

Maui

Molokai

63

22°

21°

20°

19°

160° 159° 158° 157° 156° 155°

Kaui

Oahu

Molokai

Hawaii

Hawaii – regions within islands

Kona

Kau

Puna

Kaanapali

Kualapuu

Kula

Waialua

Waiahole

Kunia

Eleele

22°

21°

20°

19°

160° 159° 158° 157° 156° 155°

Kaui

Oahu

Molokai

Maui

Hawaii

Hawaii – regions within islands

64

• δ34S

• δ18O

• Y, La, Ce, Sm, B, Al, Fe, Ni, Cu,

Rb, Sr, Mo, Ba

Provenance of Fish

Fish Hard Parts

Non lethal strategy

Otoliths Back bone

Eye lenses Scales Fin rays

http://www.google.com/imgres?imgurl=http://courses.washington.edu/chordate/453photos/skeleton_photos/fish_trunk_vert.jpg&imgrefurl=http://courses.washington.edu/chordate/453photos/skeleton_photos/anamniote_skeleton_photos.htm&usg=__Ufvg_MyJuqt5a4_tFaFb_canYX8=&h=598&w=576&sz=63&hl=de&start=3&itbs=1&tbnid=w09Z2mlxeT6L2M:&tbnh=135&tbnw=130&prev=/images?q=vertebrae+fish&hl=de&gbv=2&tbs=isch:1

function: balance, orientation, hearing

• Otolith = ear stone of the fish

• metabolically inert

•Grows in discrete layers

• Ca ↔ Sr

• Analysis by LA-ICP-MS

Sr Isotopes in Fish Otoliths

http://www.marine.maine.edu (07-07-03)

Otolith

Otolith – core: Sr-signature of the

juvenile habitat

Otolith – rim:

Sr –signature of the

adult habitat

Migration pattern

Fish provenance

Fish stock management

Population identification

Population dispersion

Age determination

Biomonitor

Temperature

Salinity

contaminationgen

Different Areas of the Otolith Represent different age times

Elemental uptake in the different fish hard parts

Adapted after Campana 1994

E.g. 80-90 % uptake of Ca

in the otolith via the gills

Time resolved analysis using LA-ICP-MS

87Sr/86Sr

River 1

River 2

Example: change of habitat (trout)

71

Anras (Dolomit)

Windbach (Gneiss)

Genetical fingerprint

Ac

hs

e 2

(3

,85

%)

Achse 1 (4,21%)

genetics (factorial correspondence analysis)

trout 2

trout 1

Element- and isotopic analysis

water Windbach

Otolith core (trout 1)

Otolith rim (trout 1)



0.707

0.708

0.709

0.710

0.711

0.712

0.713

0.714

0.715

0 1 2 3 4 5 6 7 8

87S

r/86S

r

88Sr/43Ca

Elementmuster - Forelle 1

trout 2 – Sr/Ca ratio



water Windbach





0.707

0.708

0.709

0.710

0.711

0.712

0.713

0.714

0.715

0 1 2 3 4 5 6 7 8

87S

r/86S

r

88Sr/43Ca




Anras


water Windbach





0.707

0.708

0.709

0.710

0.711

0.712

0.713

0.714

0.715

0 1 2 3 4 5 6 7 8

87S

r/86S

r

88Sr/43Ca




Anras

Windbach

Juvenile phase: groundwater

Adult phase: surface water

Comparison of fish otoliths of rainbow

trout from different fish farms

Juvenile and adult phase in the

same water

Otolithen:

100% identification of the

habitat clusters

via

23Na/43Ca, 88Sr/43Ca and 87Sr/86Sr

(Discriminant analysis)

Habitat identification fish ponds in different geological regions

Canonical variate 1

30.020.010.00.0-10.0

Can

on

ical vari

ate

2

5.0

2.5

0.0

-2.5

-5.0

DSilicous rocks surface

Calcareous rocks

groundwater

Calcareous gravel surface

near groundwater

Calcaerous rocks

surface

Zitek, A., M. Sturm, H. Waidbacher and T. Prohaska (2010).

Fisheries Management and Ecology, 17, 435-445

Water sample clusters:

0.7050

0.7070

0.7090

0.7110

0.7130

0.7150

87Sr

/86Sr

0.00

0.20

0.40

0.60

0.80

1.00

1.20

1.40

1.60

1.80

2.00

88S

r/43C

a

Salmonide: chemical life history

(age: 12 months)

I

c

e

l

a

n

d

otolith growths

1000 µm

120 µm

~4 Mon.

Eismeersaibling

Laser spot = 50 µm

Comparison of life histories

• Individual ‚chemical curriculum‘ of fish (87Sr/86Sr, Sr/Ca) • Time resolved analysis from the egg to the last months • Significant difference in the life histories





(multi)- elemental

spikes

enriched stable

isotopes

marking via elemental spikes or enriched isotopes

<< extrinsic marking >>


Enriched stable isotope tracer studies

Sr ↔ Ca

Sr Spiking

Spiking 84Sr 86Sr

• To trace element fluxes in an ecosystem

• To identify sources and sinks

• To mark a specific abiotic or biotic matter in

an ecosystem

• To monitor metabolic fluxes of an element

Enriched stable isotopic spikes AIM: Inducing a significant change of the natural variation by using an enriched spike for

Enriched stable isotope tracer studies Basic principle

0

20

40

60

80

100

84Sr 86Sr 87Sr 88Sr

ab

un

da

nce

/%

84Sr 86Sr 87Sr 88Sr

0

20

40

60

80

100

84Sr 86Sr 87Sr 88Sr

ab

un

da

nce

/%

84Sr 86Sr 87Sr 88Sr

0

20

40

60

80

100

84Sr 86Sr 87Sr 88Sr

ab

un

da

nce

/%

84Sr 86Sr 87Sr 88Sr

Enriched stable isotope tracer studies

Enriched stable isotope tracer studies Isotope pattern deconvolution (IPD)

Evaluation of the double isotope tracer Isotope pattern deconvolution

0

20

40

60

80

100

84Sr 86Sr 87Sr 88Sr

ab

un

da

nce

/%

84Sr 86Sr 87Sr 88Sr

molar fraction ratio of xSp1/xSp2 of double spike in central otolith region

0

20

40

60

80

100

84Sr 86Sr 87Sr 88Sr

ab

un

da

nce

/%

84Sr 86Sr 87Sr 88Sr 0

20

40

60

80

100

84Sr 86Sr 87Sr 88Sr

ab

un

da

nce

/%

84Sr 86Sr 87Sr 88Sr

J. Irrgeher, A. Zitek, M. Cervicek, T. Prohaska; J. Anal. At. Spectrom., 2014,29, 193-200

APPLICATION: Transgenerational marking of fish

• Ecological application Mass marking of larvae without interfering with natural spawning, dispersal

• Aquaculture (affordable marking method) Quality management (authenticity and origin)

Transgenerational marking of fish

Maternal transfer of elements to eggs

Otolith:

- first hard part developing (within the egg) - stores maternal information

After hatching, uptake of environmental information

Maternally derived area of fish otolith

The center of the otolith is created within the egg; contains the maternal information

Hatch check: visual clue for the area, where maternal information can be expected

10 µm

Primordia

Hatch check

Core

1.5 mm

Transgenerational isotopic marking of freshwater fish using a 86Sr/84Sr double spike

• Model species:

– Carp: cyprinids (100.000-300.000 eggs/kg body weight)

– Brown trout: salmonids (1.500-2.000 eggs/kg body weight)

otolith core region 50-75 µm

A. Zitek, J. Irrgeher, M. Cervicek, M. Horsky, M. Kletztl, T. Weismann, T. Prohaska (Marine and Freshwater research, in press)

Fischzucht Kreuzstein

LA-ICP-Q-MS of a single carp otolith (ca. 4440 µg 86Sr kg-1 fish)

500 µm

0.0

0.10-0.12

0.12-0.13

0.13-0.14

86Sr/88Sr

NWR193

Laser Ablation System

Nexion 300D (ICP-Q-MS)

Perkin Elmer

86Sr/88Sr natural ~0.12

He carrier gas Spot size: 35 µm Scan speed: 2 µm s-1

Rep. rate: 20 Hz

Szene schwarz probieren

Nexion 300D (ICP-Q-MS)

Perkin Elmer

NWR193

Laser Ablation System

0.0

0.10-0.12

0.12-0.13

0.13-0.14

86Sr/88Sr

86Sr/88Sr natural ~0.12

Absolute 88Sr/84Sr and 88Sr/86Sr ratios – Control fish

7.00

7.40

7.80

8.20

8.60

60

80

100

120

140

160

1800

40

80

12

0

16

0

20

0

24

0

28

0

32

0

36

0

40

0

44

0

48

0

52

0

56

0

60

0

88S

r/8

6S

r

88S

r/8

4S

r

µm

laser line

No change of natural Sr isotopic signature


No isotope spike - pure saline solution injected

7.00

7.40

7.80

8.20

8.60

60

80

100

120

140

160

1800

40

80

12

0

16

0

20

0

24

0

28

0

32

0

36

0

40

0

44

0

48

0

88S

r/8

6S

r

88S

r/8

4S

r

µm

laser line

Spike dose: 1.3 mg 84Sr/kg fish 5.5 mg 86Sr/kg fish

Absolute 88Sr/84Sr and 88Sr/86Sr ratios – Spiked fish

Significant change of natural Sr isotopic signature in the core region of otoliths:

Sr tracer: 0.1 – 3.5 %


Deconvolved molar fraction ratio of the double spike (xSp-86/xSp-84)

0.00

1.00

2.00

3.00

4.00

5.00

6.00

7.00

8.00

9.00

10.00

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 mean

x Sp-86/x

Sp-84inthecorearea

otolithnumber

tracer solution 4

tracer solution 3

tracer solution 2

tracer solution 1


0.00

1.00

2.00

3.00

4.00

5.00

6.00

7.00

8.00

9.00

10.00

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 mean

x Sp-86/x

Sp-84inthecorearea

otolithnumber

uc (k = 1) 3.7 %


0.00

1.00

2.00

3.00

4.00

5.00

6.00

7.00

8.00

9.00

10.00

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 mean

x Sp-86/x

Sp-84inthecorearea

otolithnumber

uc (k = 1) Repea bility(within-sample-precision)

Blankcorrec on

Reproducibility(within-batch-precision)

Instrumentalisotopicfrac ona on

Rbinterferencecorrec on

1.3 % 3.7 %


0.00

1.00

2.00

3.00

4.00

5.00

6.00

7.00

8.00

9.00

10.00

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 mean

x Sp-86/x

Sp-84inthecorearea

otolithnumber


Blankcorrec on




1.3 %

Repea bility(within-sample-precision)

Blankcorrec on




5.1 % 3.7 %


0.00

1.00

2.00

3.00

4.00

5.00

6.00

7.00

8.00

9.00

10.00

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 mean

x Sp-86/x

Sp-84inthecorearea

otolithnumber


Blankcorrec on




1.3 %

Repea bility(within-sample-precision)

Blankcorrec on




18.4 % Repea bility(within-sample-precision)

Blankcorrec on




5.1 % 3.7 %

Requirements

Requirements elementsl/isotopic fingerprint

Instrumentation

Infrastructure

Personell

Consumables


Instrumentation (multi-elemental fingerprinting)

ICP-AES (30.000 – 8.000 U$) / 5000 – 10000U$/year

ICP-QMS (70.000-40.0000 U$)/ 10000 – 15000 U$/Year

Instrumentation (isotope ratio analysis)

(ICP-QMS (70.000-40.0000 U$)/ 10000 – 15000 U$/Year)

(ICP-SFMS (300.000 – 500.000 U$/ 10.000 – 15.000 U$/year)

TIMS (250.000 – 500.000 U$/ 10.000 – 15.000 U$/year)

MC-ICP-SFMS (500.000-800.0000 U$)/ 15.000 – 20.000 U$/Year


Instrumentation (multi-elemental fingerprinting)

ICP-AES (30.000 – 8.000 U$) / 5000 – 10000U$/year

ICP-QMS (70.000-40.0000 U$)/ 10000 – 15000 U$/Year

Instrumentation (isotope ratio analysis)

(ICP-QMS (70.000-40.0000 U$)/ 10000 – 15000 U$/Year)

(ICP-SFMS (300.000 – 500.000 U$/ 10.000 – 15.000 U$/year)

TIMS (250.000 – 500.000 U$/ 10.000 – 15.000 U$/year)

MC-ICP-SFMS (500.000 – 800.0000 U$)/ 15.000 – 20.000 U$/Year


Infrastructure / consumables

Cleaning and chemicals (100.000 – 200.000) / 10.000 U$/year

Sample preparation (100.000 – 300.000 U$) / 20.000U$/year

Analytical laboratory (500.000 – 1.000.000 U$) / 10.000U$/year


Collaboration

Isotopic measurements (light stable isotopes) 50 – 200 U$ / sample

Isotopic measurements (heavy stable isotopes) 50 – 200 U$ / sample

Elemental fingerprint (multielement) 50 – 250 U$ / sample

Acknowledgements

START Projekt 267N11 ‘VIRIS‘

P21404-B17 ‘IsoMark’

http://www.fwf.ac.at/index.asp

food provenance by elemental and isotopic fingerprint methods · food provenance by elemental and...

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