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Fate of TBT during seafood cooking Paolo Massanisso*, Fabiana Di Rosa*, Frank Willemsen° and Roberto Morabito* *ENEA/PROT - Italy °IVM – The Netherlands [email protected] ICEBAMO 2003 Pau December 3 - 5, 2003

Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

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Page 1: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

Fate of TBT during seafood cooking

Paolo Massanisso*, Fabiana Di Rosa*,Frank Willemsen° and Roberto Morabito*

*ENEA/PROT - Italy°IVM – The Netherlands

[email protected]

ICEBAMO 2003Pau

December 3 - 5, 2003

Page 2: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier
Page 3: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

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Page 4: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

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Page 5: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

“ONE OF THE MAIN ISSUE FOR MARINE ENVIRONMENT IMPACT”

BUTIS IT ALSO AN ISSUE FOR HUMAN

HEALTH?

TBT

Page 6: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

Human exposure to Organotins

Page 7: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

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Quality of Life and Management of Living Resources Contract QLK1-CT- 2001-01437

Sources, consumer exposure and risks of organotin contamination in seafood - OT-SAFE

(Starting date 01/12/2001 – Ending date 31/05/2004)

Key action 1: Food, Nutrition and Health

Page 8: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

OT-SAFE CONSORTIUM

CEFASB. Jones - UK

University of Umea W. Frech - SE

University of HuelvaJ.L. Gomez Ariza - ES

SIUP. Fodor – HU

GALABJ. Kuballa - DE

Agr. Res. Centre K. Cooreman - BE

University of Pau F. Pannier - FR

University of Porto M. Santos – PT

ENEA R. Morabito - IT

Aegean University N. Thomaidis – GR

IVMJ.W. Wegener (Coord.) - NL

SUBCONTRACTORSMAIN PARTNERS

Project officerA. Boenke - EU

Page 9: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

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• Toxicity– TDI - Tolerable daily intake (0.25 µg/day/bw)

• National food consumption– TARL – Tolerable Average Residue Level

• Concentration levels on seafood for human consumption

• Degradation to less harmful compounds during cooking

Page 10: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

OT-SAFE WORKPACKAGES• WP1 – University of Pau – FR/IVM - NL

– Building an EU-wide database on TBT in seafood at major European seafood farms and fishing grounds.

• WP2 – ENEA - IT– Studying the possible TBT level reduction in

seafood during various cooking procedures. • WP3 – IVM - NL

– Assessing whether there is a risk for consumers associated with the consumption of TBT-containing seafood sold on the European market.

Page 11: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

WORKPACKAGE 2Studying the possible TBT-level reduction in seafood during various cooking procedures.

• Evaluation of TBT degradation during home cooking– Carried out by ENEA – IT

• Evaluation of TBT degradation duringindustrial cooking– Carried out by IVM – NL

Page 12: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

HOME COOKING

• 15 kg of mussels from a mussel farm were cleaned and randomly subdivided into four groups.

– Samples from one group were directly analysed whereas samples from the other three groups have been cooked following different European cooking recipes (UK, NL, PT, GR, IT).

– Ingredients without any presumable effect on TBT degradation (garlic, pepper, etc.) have not been considered to minimize the matrix problems.

– Ingredients that could influence the cooking temperature or have a potential extraction solvent effect (oil, wine) have been considered.

Page 13: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

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Page 14: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

15 Kg o f m usse ls

R aw Frying M W Steam ing Boiling

S H E LLIN GS H E LLIN G

H O M O G E N E IZATIO NH O M O G E N E IZATIO N

S TO R A G E-20 °C

S TO R A G E-20 °C

G C -M S AN A LYS ISG C -M S AN A LYS IS

LIQ U IDFR A C TIO N

LIQ U IDFR A C TIO N

Page 15: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

ANALYTICAL PROCEDURE FORMUSSELS AND SEDIMENT

SAMPLEca 500 mg dry weight add 50-500 ng

TPrT as internal std.

SONICATION

3tropolone - repeat twice

LIQUID/LIQUID PARTITIONINGadd 150 ml water - 30 ml CH2Cl2

SOLVENT EXCHANGEto 1 ml isooctane by a gentle stream

of N2

GRIGNARD DERIVATIZATION1 ml PeMgBr 2M in diethyl ether

sediments/biotaSILICA GEL/FLORISIL CLEAN UP1 g in a Pasteur pipette elution with

2.5 ml of hexane:toluene (1:1)

GC ANALYSIS(FPD or MS)

15 ml CH OH/1 ml HCl conc./0.03%

Page 16: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.000

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Page 17: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

TBT, DBT and MBT in 250 g of mussels before and after cooking in microwave oven

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

Raw sample MW-1 MW-2

ng TBT

DBT

MBT

TBT, DBT and MBT in 250 g of mussels before and after cooking in frying pan

0

4000

8000

12000

16000

20000

Rawsample

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DBT

MBT

TBT, DBT and MBT in 250 g of mussels before and after cooking by steaming

0

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8000

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16000

20000

Raw sample ST-1 ST-2 ST-3

ng TBT

DBT

MBT

TBT, DBT and MBT in 250 g of mussels before and after boiling at increasing time

0

4000

8000

12000

16000

20000

Rawsample

K-5 K-10 K-20 K-30 K-60

ngTBT

DBT

MBT

Page 18: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

TBT in 250 g of mussels before and after different cooking procedures

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DBT in 250 g of mussels before and after different cooking procedures

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Page 19: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

TBT CONTROL CHARTBCR 477

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X

X+3sX+2s

X-2s

X-3s

In-House RM

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Page 20: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

INDUSTRIAL COOKING• 10 Kg of mussels from the same mussel farm

have been sent to IVM and divided into twelve subsamples. – Three kept in the freezer – Three analysed in singlefold – Six combined to a single batch and steamed in the

industrial mussel plant.

• After steaming, the mussels were divided into six subsamples. – Three analysed in singlefold – Three put in a glass jar with vinegar and

pasteurised and then analysed in singlefold.

Page 21: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

Industrial cooking

0

2000

4000

6000

8000

10000

12000

14000

Raw sample Steamed Steamed,pasteurised in

vinegar

ng

TBT

DBTMBT

Comparison of TBT, DBT and MBT, as cations, in 80 g of shelled mussels before and after industrial cooking�

10400 9860 7940

2020 2010 1660

540 410 490

Page 22: Fate of TBT during seafood cooking...University of Huelva J.L. Gomez Ariza - ES SIU P. Fodor – HU GALAB J. Kuballa - DE Agr. Res. Centre K. Cooreman - BE University of Pau F. Pannier

CONCLUSIONS• The study on the effect of short-term heating

showed that TBT is not significantly degraded by seafood cooking and consequentely there isn’t a significant reduction of the potential impact on human health.

– Home Cooking by steaming and boiling leads to a TBT degradation never higher than 30% and only in case of frying pan cooking the TBT concentration drop down to the 40% of the original content.

– Industrial steaming procedure does not affect at all TBT stability and only in the case of a following pasteurizartion in vinegar, a slight degradation of TBT was observed (20%).