Professional Documents
Culture Documents
,
. ,
E
n
n
n
n
n Case study:
n
EY
178/2002:
(EFSA)
( )
: ,
,
,
EY
( : 93/99/)
:
,
-
.
Enterprise Directorate-General
:
:
1.
2.
3. HACCP
4.
5.
( 96/23/)
n
( )
:
:
( )
(RASFF)
;
n :
():
(, , , )
():
n :
(.. ..)
n :
H
,
link :
http://www.efet.gr/
&
:
http://www.efet.gr/health.html
: ,
,
,
,
RASFF
n
44%
27% } 71%
17%
:
- EU
-
- &
- (non-EU)
27%
25%
17%
11%
RASFF
n
:
- (Seafood)
- ,
- , ,
30%
15%
15%
:
- (Sudan dyes, Para Red)
- (Cd, Hg, Pb)
- (NFs, CAP, MG)
- (sulfite, histamine)
- (OPs, dimethoate)
- (ITX)
21%
16%
14%
11%
7%
6%
.
n
.
n
n
n
:
(
)
(
): - ,
, /
.
:
,
, -
:
http://www.efsa.europa.eu/
EFSA
n
2004 2009:
n EFSA
Journal:
http://www.efsa.europa.eu/cs/Satellite/en/efsajournal/scdoc/e831.htm?emt=1
EFSA Journal
:
n
:
n
Journals:
:
http://www.who.int/ipcs/food/jecfa/en/
10
:
http://www.inchem.org/
(risk
assessment) 4 :
(i) ,
(ii) ,
(iii) ,
(iv) .
11
WHO:
n
n
n
n
n
,
,
(risk management)
(risk
communication)
.
12
n
n
n
n
n
n
n
n
(, ,
) (Additives)
(flavourings)
(Contaminants)
-
13
http://ec.europa.eu/food/food/chemicalsafety/index_en.htm
http://legislation.selamat.net/default.aspx
14
Contaminants
(Pb, Cd, Hg, inorg.Sn)
n (3-MCPD)
n PAHs
n & PCBs
n
n (, ,
, Fusarium)
n
Contaminants
n
-
Ethyl Carbamate
15
-
n
1881/2006/
(MRL) Pb, Cd g, Sn,
, , , PCBs,
3--1,2- (3-MCPD),
.
1881/2006/
n
Pb ( MRL)
0,02 mg/Kg
0,1 mg/Kg
0,5 mg/Kg
0,2 mg/Kg,
, , , , ,
, , .. 0,4 mg/Kg
0,5 mg/Kg,
1,5 mg/Kg,
1,0 mg/Kg
, , ,
, , ..
16
1881/2006/
n
Cd ( MRL)
0,05 mg/Kg,
0,2 mg/Kg
0,5 mg/Kg
1,0 mg/Kg
0,05 mg/Kg,
, , , , , ,
, , ..
0,1 mg/Kg
0,5 mg/Kg,
1,0 mg/Kg,
1,0 mg/Kg
, , ,
1881/2006/
n
Hg ( MRL)
0,5 mg/Kg,
, , , ,
, , , , ,
, ..
1,0 mg/Kg
17
333/2007
Pb, Cd, Hg,
Sn, 3-MCPD [a]
n:
, , ,
, , .
n:
.
.
333/2007
:
.
1 kg, .
:
. ,
.
18
333/2007
n
:
, ,
, .
( )
:
.
(
, ,
, )
333/2007
n
:
1. :
, (1
kg).
2. :
(kg)
<50
50 500
>500
10
19
333/2007
n
:
3. :
1 25
25 100
5%, 2
(2-5 )
5%, 10
(5-10 )
>100
333/2007
1/10
RL, MRL Pb <0,1 mg/Kg.
, 1/5.
1/5 RL,
MRL Pb <0,1 mg/Kg. ,
2/5.
()
Horratr HorratR
2 ( )
80-120% ( CRM)
20
n
n
n
n
n
n
: Pb, Cd, Hg
: As TBT (OTCs)
(Pb)
: , Pb,
,
(Cd)
: , (Pb,Cu),
(, ,
, , )
(Hg)
: ,
(, , ,
, , ,
, , ,
)
21
( )
Zn ( )
( 2)
, (MeHg)
10 - 50 g/d (5-20% )
(50-1400 ng/g)
90% CH3Hg (90% )
22
WHO:
n
n
n
PTWI: 25 g/kg bw (, , )
TDI: 3,5 g/Kg bw
13804:2002
Foodstuffs Determination of trace elements
Performance criteria and general considerations
n
n
333/2007
: , ,
() (
Cr, Ni, Fe, Mo,
), (), ,
.
: , (
!)
: -40C .
-, ,
, .
23
13804
Foodstuffs Determination of trace elements
Performance criteria and general considerations
n
:
:
:
( )
, :
.
.
.
: (
). .
13804
Foodstuffs Determination of trace elements
Performance criteria and general considerations
n
:
stomacher ( ).
: + ,
:
. ,
. ,
.
: .
.
: ,
, 5 min.
, .
24
13804
Foodstuffs Determination of trace elements
Performance criteria and general considerations
n
: (supra pur, Traceselect ..).
, ,
( > 5 cm)
: , .
: . , ,
PTFE, . .
(PFA).
: ,
, 10% HNO3
. DD-DI (
)
: Al, Cr, Zn, Fe, Cu .
.
13804
Foodstuffs Determination of trace elements
Performance criteria and general considerations
n
25
n
n
n
n
ISO:
: , , generic
AOAC: 70.
.
: (
)
.
LK
pr 14082: Pb, Cd, Zn, Cu, Fe, Cr / AAS/ Dry ashing
pr 14083: Pb, Cd, Cr, Mo / AAS/ Pressure digestion
pr 14084: Pb, Cd, Zn, Cu, Fe / AAS/ Microwave
digestion
:
n (Dry ashing)
n (Pressure digestion)
n (Microwave
digestion)
26
Pt (50ml)
10-20 g (10mg)
: . 100C 50C/h 450C (24h)
: , 1-3 ml H2O,
450C 1-2 h,
- .
5 ml HCl, ,
10-30 ml 3
(FAAS, GFAAS, ICP-AES, ICP-MS)
- ( UV,
200C)
.
27
0,2-0,5 g (< 1 g)
.
n 4-5 ml HNO3 + 1-2 ml H2O2
n :
:
n
(W)
(min)
250
3-5
600
450
20-25
As
As As(III) As(V)
.
: 10 g L-1
As,
( As)
As
(2002)
?
MRL As ?
28
29
As
As(III)
DMAs
AsBet
0,06
0,26
0,30
0,20
0,11
0,25
5,98
3,50
2,96
5,06
22,59
23,11
11,28
11,29
1,24
18,04
5,97
2,72
24,18
22,11
10,57
5,21
7,18
5,51
0,10
0,15
0,20
0,30
0,27
0,40
0,35
0,35
0,87
1,13
1,28
1,42
1,81
1,92
1,36
1,58
1,19
3,56
0,55
0,31
0,73
1,42
sample
9,09
mussels
Gr01
6,29
mussels
Gr02
6,02
mussels
Gr03
7,88
mussels
Gr04
28,21
mussels
Gr05
23,65
Anchovy
Gr06
11,28
Anchovy
Gr07
11,60
Anchovy
Gr08
1,24
Seabass
Gr09
18,04
Squid
Gr10
8,27
mussels
Gr15
2,92
24,48
Anchovy
Gr17
22,38
Anchovy
Gr18
10,97
Sardines
Gr19
5,21
Seabass
Gr20
7,53
Sardines
Gr23
5,86
Sardines
Gr24
30
As
As:
-
- , (hijiki)
- (
, bran, germ)
- As
- 70% As
- 70% As
As(V) As(II)
As
n
EFSA (2010):
31
, ,
.
I.
(insecticides)
(herbicides)
(fungicides)
II.
32
.
:
:
:
, .
:
.
:
.
(ADI).
33
396/2005 :
.
299/2008:
1 2008
396/2005 MRLs
.
470/2009: MRLs
.
34
http://ec.europa.eu/sanco_pesticides/public/index.cfm
http://www.pesticides-online.com/
35
1.
2.
3.
4.
5. -
6.
7.
(NSAIDs)
36
:
n
n (
-)
n ()
n
(phenylbutazone, ,
)
: 2377/90/E..
( IV)
(Maximum Residue Limit, MRL)
v
v
470/2009/E..
MRL 37/2010/E..
:
96/22/E.. 96/23/E..
A:
:
:
2002/657/..
37
http://www.codexalimentarius.net/mrls/vetdrugs/jsp/vetd_q-e.jsp
12
2002
96/23/E
2002/657/
38
.
1 96/23/E
LC GC MS
A B
on-line off-line
.
3 ( B) 4 A)
LC GC IR
A B
LC -DAD
LC-FLD
2-D TLCUV/VIS
HPTLC
.
GC- FID
LC-UV/VIS
,
.
..
.
.
, (
),
.
,
.
39
( ),
,
.
n
:
() ,
.
.
(on-line)
(off-line).
GC-MS
LC-MS
.
LC.
:
,
,
0,5 % GC 2,5 % LC.
40
A
MS,
(full scan)
(SIM), MS-MSn,
(SRM), MS MSMSn .
.
(% )
EI-GC-MS
()
> 50 %
10 %
20 %
> 20 % 50 %
15 %
25 %
> 10 % 20 %
20 %
30 %
10 %
50 %
50 %
.
T MS
(LR)
1,0
LR-MSn
1,0
LR-MSn
1,5
HRMS
2,0
HR-MSn
2,0
HR-MSn
2,5
41
:
10 %.
SIM: A I
96/23/, 4 .
B
96/23/, 3
(n = )
2 (EI) + 2 (CI)
2 ( A) + 2 ( B)
LC-MS
GC-MS-MS
1 2
LC-MS-MS
1 2
GC-MS-MS
2 , 1
LC-MS-MS
2 , 1
LC-MS-MS-MS
1 , 1 , 2 . 2
5,5
HRMS
2n
GC-MS LC-MS
2+2
GC-MS HRMS
2+1
42
2002/657/C
:
1.
6.
2. /
7.
3.
8.
4.
9.
5. E
1.
n
n
n
i.
ii.
iii.
20
43
2./
6 CRM
n ,
(%)
(%) =
x 100 /
n
CRM
:
n
18
6
1, 1.5 2
MRPL 0.5, 1, 1.5 MRL
% =100 x /
CV 6
44
< 1g/kg
> 1g/kg 10g/kg
> 10g/kg
-50% +20%
-30% +10%
-20% +10%
3.
(CV)
,
,
Horwitz:
CV=2(1-0.5log C)
C (g/g)
10
:
< 100g/kg
45
CV < CV
n
MRL :
CV < CV
0.5MRL
4.
,
Youden
46
5.
(.40).
A.
n
:
-20oC
10
+4oC
10
+20oC
10
10
47
100%
(%) = Ci x 100/Cfresh
Ci = i
Cfresh =
B.
5
-20oC
1, 2, 4 20
48
6.
n
n
n
:
6 1MRPL 0.5MRL
6 1.5MRPL 1MRL
6 2MRPL 1.5MRL
,
, CV%
2 (54 )
CV
7.
n
n
n
:
6 1MRPL 0.5MRL
6 1.5MRPL 1MRL
6 2MRPL 1.5MRL
2 (54 )
,
CV(%)
49
8. (CC)
MRL CC
:
i.
MRL . ,
CC = CMRL + 1.64 SD . (=5%)
ii. 20
MRL.
,
CC = CMRL +1.64 SD
(=5%)
9.
i.
ii.
MRL CC
:
MRL .
. ,
CC = CC + 1.64 SD . (=5%)
20
. ,
CC = CC + 1.64 SD
(=5%)
50
10.
n
i.
ii.
:
5
( 0)
,
.
51
n
n
n
n
n
n
n
n
n
(Aspergillus)
(Aspergillus & Penicillium)
(Fusarium)
& (Fusarium)
(Aspergillus, Penicillium & Byssochlamys)
Ergot
Citrinin
Cyclopiazonic acid
Monilinoformin
( )
http://www.chem.uoa.gr/chemicals/chem_aflatoxins.htm
http://ec.europa.eu/food/food/chemicalsafety/foodcontact/index_en.htm
52
(BPA)
H3C
HO
CH3
OH
(65%)
(25%)
(10%)
2,2--[4-o]
: 228
(BPA)
()
;
( >90C)
( )
-
53
X
EDCs (Endocrine Disrupting Chemicals)
( 17- (2)
( )
(EDCs)
-
.
,
, , ,
.
54
,
.
-,
' ,
.
().
55
()
n
()
,
.
,
.
56
()
n
-
, ,
,
(metabolic clearance).
, ,
,
.
,
.
,
(sexual development).
57
58
,
,
(mimics - agonists).
,
,
' ,
(Blockers, antagonists, antiandrogens or anti-estrogens).
w (Stimulators). -
w (Hormone flushers).
.
.. PCBs ,
.
w (Enzyme flushers).
,
,
.
w / (Destructors).
.
59
EDCs
n
(intact)
,
European Commission, 1996
, , ,
,
, ,
/
US EPA, 1997
60
()
(Steroids)(?)
(Alkylphenols)
(Bisphenol A)
(Phthalates)
(Pesticides)
(PCBs)
(PAHs)
TBT ( )
(daidzein, genistein)
M ()
.
EDCs
Estrone
17-Estradiol
17-Ethynylestradiol
n(Cl)
Benzo(a)pyrene
(Cl)n
PCBs
61
EDCs
Triclosan
DDT
Bis(2-ethylhexyl)phthalate (DEHP)
H3C
CH3
OH
HO
4-n-Nonylphenol
4-tert-octylphenol
Bisphenol A
(OTs)
R(n)SnX(4-n)
,
R = ( , , )
X = .. , ,
n = 1 4
MBT, DBT, TBT
MPhT, DPhT, TPhT, ,
- - OTs
PVC
- OTs
( ,
)
62
OTs
n
n
n
n
imposex
OTs
(UV)
n
n
(
)
63
OTs
105
OTs
IMPOSEX
Ca2+
64
OTs
1.
2.
:
PVC
: ,
, ,
,
,
n
n
OTs?
EU (MRL)?
65
OTs
- TDI (Tolerable Daily Intake
)
[TDI (g kg )] [ (60kg )]
[ (g )]
-1
-1
-1
, 1998
1999 (Household budget survey)
6258 .
.
.
(95%)
(g -1 -1).
, 1999 (Food Balance Sheets)
66
n
n
n
n
n
' (, ,
, , , , ,
).
' (, ,
, , , , ).
' (, , ,
, , ).
(', ' ' ).
(, ,
, , , ).
(, ,
, , , ).
,
, , , .
(1999)
(g -1 -1)
(g -1 -1)
th
(95th)
(95 )
(%)
6,0
36
41
95
15
6,1
36
37
89
16
18
71
41
95
41
5,5
36
39
89
14
2,6
18
37
95
6,4
3,4
24
31
71
9,8
1,5
10
12
34
13
45
247
280
672
67
: 98
: n=6 (3 , 3 )
: n=2 (2 )
: n=13 (8 , 5 )
: n=13 (5 , 1 , 4 , 2
, 1 )
: n=37 (8 , 6 , 19 , 3
, 1 )
: n=19 (5 , 5 , 1 ,
1 , 3 , 4 )
: n=8 (4 , 2 , 1 , 1
)
OTs
(ng g-1)
(n=6)
<4 12,5
7,92
7,50
6,90
(n=2)
29,3 31,2
27,55
27,55
27,31
(n=13)
<4 491
74,11
38,00
27,36
(n=13)
<4 54,2
9,40
7,50
5,81
(n=37)
<4 109
29,79
17,00
17,10
(n=19)
<1 29,0
5,44
2,00
3,59
(n=8)
<15
<1 491
24,93
7,50
10,13
68
D (ng g-1)
(n=6)
<13
(n=2)
<13
(n=13)
1,00 20,0
5,45
5,00
4,20
(n=13)
<10 371
67,62
6,50
21,57
(n=37)
5,00 366
43,11
15,00
18,84
(n=19)
<1 230
49,05
6,50
8,51
(n=8)
<10 1117
173,1
49,40
36,61
<1 1117
50,00
6,50
12,61
M (ng g-1)
(n=6)
1,00 17,3
4,72
2,75
2,74
(n=2)
<7
(n=13)
1,00 49,1
7,08
1,50
2,74
(n=13)
<7 21,5
6,54
3,50
5,13
(n=37)
1,10 151
17,77
7,87
7,84
(n=19)
<1 30,9
7,16
3,50
3,09
(n=8)
<6 18,9
5,33
3,50
4,23
<1 151
10,70
7,50
4,72
69
(n=6)
<13
(n=2)
<13
(n=13)
4,40 49,0
10,49
6,00
7,69
(n=13)
<13
(n=37)
1,80 201
18,24
5,00
8,30
(n=19)
<1 90,4
13,86
5,00
4,30
(n=8)
<13
<1 201
12,64
5,00
6,37
(n=6)
(n=2)
(n=13)
(n=13)
(n=37)
(n=19)
(n=8)
TBT
72
100
80
18
39
24
DBT
12
66
43
56
90
MBT
28
16
18
20
10
BTs
100
100
100
100
100
100
100
1.
2. TBT
70
OTs TARL
(n=98)
COTs
(ng g-1)
TARL
(ng g-1)
TARL
(ng g-1)
%TARL
%TARL
TBT
10,13
348,0
63,0
2,9
16,0
DBT
12,61
348,0
63,0
3,6
20,0
MBT
4,72
348,0
63,0
1,4
7,5
TPhT
6,37
348,0
63,0
1,8
10,1
BTs
27,46
348,0
63,0
7,9
43,6
OTs
33,83
348,0
63,0
9,7
53,7
Uncertainty
~20%
Uncertainty (?)
Adopted by:
71
1 :
(g kg -1 -1) =
ADIbw (Average Daily Intake) :
-1
-1
-1
[ADIbw ] = [ (g g )] [ (g )]
[ (70kg)]
(g kg -1 -1) =
MDIbw (Maximum Daily Intake) :
-1
-1
-1
[MDIbw ] = [ (g g )] [ 95% (g )]
[ (70kg)]
2 :
(g/kg /) =
ADIbw,c (Average Daily Intake) :
-1
-1
-1
[ADIbw, c] = [ (g g )] [ (g )]
[ (70kg)]
(g/kg /) =
MDIbw,c (Maximum Daily Intake)
-1
-1
-1
[MDIbw, c ] = [ (g g )] [ 95% (g )]
[ (70kg )]
72
(g kg
-1 -1)
TBT
DBT
MBT
TPhT
BTs
OTs
0,0024
0,0024
0,0088
0,0108
BTs
OTs
0,0201
0,0246
0,0024
(95%)
0,0160
0,0070
0,0011 0,0007
0,0020
(95%)
0,4980
0,0203 0,0497
0,0497
5%
:
512.630
199% TDI
(g kg
-1 -1)
TBT
DBT
0,0160
0,0025
0,0016 0,0045
(95%)
0,6664
0,0271
0,0666 0,0665
267% TDI
MBT
TPhT
5% 41%
: 210.180
73
(g kg
-1 -1)
TBT
DBT
MBT
TPhT
BTs
OTs
0,0032
0,0120
0,0029
0,0181
0,0181
(95%)
0,0689
0,4719
0,0273
5% 14%
: 71.770
189% TDI
(g kg
-1 -1)
TBT
0,0090
(95%)
0,1484
DBT
199% TDI
MBT
TPhT
BTs
OTs
0,0275
5% 6,4%
: 32.808
74
TBT
0,0016
0,0038 0,0014
0,0019
(95%)
0,0294
0,2332 0,0313
0,0917
0,0063 0,0007
(95%)
0,5425 0,0092
DBT
MBT
TPhT
217% TDI
BTs
OTs
0,0067 0,0086
0,0070 0,0070
5% 13%
: 66.640
(g kg -1 -1)
(g/kg /)
(g kg
-1 -1)
0,70
0,60
0,50
TBT
0,40
DBT
0,30
MBT
0,20
TPhT
0,10
TDI
0,00
(n=6)
(n=2)
(n=13) (n=13) (n=37) (n=19)
(n=8)
75
TBT
Degradation by
boiling
18000
16000
MW
steaming
14000
Pan fried
wine
ng
10000
oil
12000
FP-2
FP-3
8000
6000
4000
2000
0
Raw
MW- 1
MW- 2
FP-1
FP- S1
FP- S2
ST- 1
ST-2
ST- 3
K- 5
K- 10
K-20
K- 30
K- 60
sample
TBT
Industrial cooking
14000
12000
10000
TBT
ng
8000
DBT
6000
MBT
4000
2000
0
Raw sample
Steamed
Steamed,
pasteurised in
vinegar
76
EFSA adoption
n
n
( - ?)
(, ,
MRLs, TDIs,
PTWI, ALARA)
( ,
, )
( )
77
,
,
(emerging contaminants)
(EFSA, SANCO)
:
,
1.
Pb , ,
.
2.
(Pb)
Zeeman (Zeeman
Electrothermal Atomic Absorption Spectrometry, ZETAAS).
283.3 nm Pb,
.
78
3.
(3)
(Pb)
4.
(MilliQ grade, Millipore).
(supra pur 3).
Pd-Mg 1g L-1 0,6 g L-1 . 100 L
Pd 60 L Mg
1 mL
.
5.
5.1.
.
..
5.2.
. PerkinElmer 4110ZL
(Transversely Heated
Graphite Atomizer, THGA) Zeeman.
79
6.
6.1.
,
6.2
10,0 g L-1.
, .
7.
:
[Pb] (g/g) = CPb (g/L) V (L)/ m (g)
8.
9.
10.
11.
80
ntho@chem.uoa.gr
http://trams.chem.uoa.gr
81