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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
ICEBAMO 2003Pau
December 3 - 5, 2003
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“ONE OF THE MAIN ISSUE FOR MARINE ENVIRONMENT IMPACT”
BUTIS IT ALSO AN ISSUE FOR HUMAN
HEALTH?
TBT
Human exposure to Organotins
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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
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
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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
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.
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
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.
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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
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%
6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.000
500
1000
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2500
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3500
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Time-->
Abundance
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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
FP-1 FP-2 FP-3 FP-S1 FP-S2
ng
TBT
DBT
MBT
TBT, DBT and MBT in 250 g of mussels before and after cooking by steaming
0
4000
8000
12000
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
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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MBT in 250 g of mussels before and after different cooking procedures
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Total butyltins in 250 g of m ussels before and after different cooking procedures
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TBT CONTROL CHARTBCR 477
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X-2s
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In-House RM
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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.
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
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%).