The Plastic Planet: Antimony in PET - Bottles

N ie d e r r h e in
U n iv e r s it y
o f A p p l ie d S c ie n c e s
I n s tru m e n te lle u n d U m w e lts c h u tz a n a ly tik
J rg e n S c h ra m
T h e p la s t ic p la n e t
A n t im o n y in P E T - b o t t le s
J rg e n S c h ra m 1
, J a n K n o o p 1 , U w e O p p e rm a n n 2
1
J rg e n S c h ra m
In s t ru m e n t a l & E n v ir o n m e n t a l A n a ly t ic s
N ie d e r r h e in U n iv e r s it y o f A p p lie d S c ie n c e s
F r a n k e n r in g 2 0
4 7 7 9 8 K r e f e ld
G e rm a n y
2
U w e O p p e rm a n n
S h im a d z u E u r o p a G m b H N ie d e r r h e in
A lb e r t - H a h n - S t r . 6 -1 0
4 7 2 6 9 D u is b u r g
U n iv e r s it y
G e rm a n y o f A p p l ie d S c ie n c e s
N ie d e r r h e in
A n t im o n y in e n v ir o n m e n t
U n iv e r s it y
J rg e n S c h ra m
A n t im o n y ( S b )
c o n t e n t in f o o d
m in e r a l w a t e r 1 , 2 g / l
f r u it ju ic e 1 3 g / l
n o t e s s e n t ia l
h ig h ly t o x ic h a lf m e t a l
lim it v a lu e E U 5 g / l
N ie d e r r h e in
A n t im o n y a s c a t a ly s t
U n iv e r s it y
J rg e n S c h ra m
P o ly e t h y le n t e r e p h t h a la t
S b 2 O 3 a s c a t a ly s t in P E T - p r o d u c t io n
- p o t e n t ia l o f c a n c e ro g e n y
- f o r b id d e n in J a p a n (= > G e O 2)
- t y p ic a l c o n t e n t : 1 0 0 -4 0 0 m g /k g
- m ig r a t io n lim it : < 0 ,0 5 m g /k g
N ie d e r r h e in
U s e o f p la s t ic s in E u r o p e 2 0 0 7
U n iv e r s it y
J rg e n S c h ra m
p a c k a g in g
b u ild in g
a u t o m o t iv e
e le c t r o n ic s
o th e r
N ie d e r r h e in
D e t e r m in a t io n o f S b in t h e P E T
U n iv e r s it y
J rg e n S c h ra m
G F A A S
g ra p h it fu rn a n c e a to m ic
a b s o rp tio n s p e c tro m e try
- v a lid a b le m e th o d
- d ig e s tio n n e c e s s a ry
- tim e c o n s u m in g
2 m m
c (S b )= ? ? ?
R F A
x -ra y flu o re s c e n c e
s p e c tro m e try
- N O T v a lid a b le
- " n o " s a m p le p re p a ra tio n
- fa st
N ie d e r r h e in
M ic r o w a v e d ig u s t io n f o r G F A A S
U n iv e r s it y
J rg e n S c h ra m
M a rs X p re s s (F a . C E M ) M a rs 5 (F a . C E M )
Tm ax 2 0 0 C Tm ax 3 0 0 C
T e m p . R a m p H a lte n
2 3 0 C 2 5 m in 2 0 m in
S b -c o n te n d [m g /k g ]
M e th o d s to ra g e P E T 1 P E T 2
1 0 m l H N O 3 (M a rs 5 ) 1 d a y 2 4 1 2 3 0
lo n g e r te m p e r a tu r e a p p lic a tio n
c h a n g e o f re a g e n ts : H N O 3 -H 2 O 2
d ilu tio n ~ fa k to r 2 5 0 ? u ltr a w a v e s u r fa c e c le a n in g
s h o r t s to r a g e tim e
8 m l H N O 3 + 2 m l H 2 O 2 0 d a y s 2 4 1 2 2 7
(M a rs E x p re s s )
N ie d e r r h e in
G r a p h it e f u r n a c e A A S
U n iv e r s it y
J rg e n S c h ra m
A A -7 0 0 0 G S h im a d z u
N ie d e r r h e in
M e th o d G F A A S
U n iv e r s it y
J rg e n S c h ra m
T e m p . [C ]
3 0 0 0
2 5 0 0
2 0 0 0
1 5 0 0
1 0 0 0
5 0 0
0
0 1 0 2 0 3 0 4 0 5 0 6 0 7 0
Z e it [s e k .] S ta n d a rd N e u ( n o r m a l) N e u ( k o m p le x l)
g r a p h it e t u b e : W - p la t f o r m
N ie d e r r h e in
M e th o d G F A A S
U n iv e r s it y
J rg e n S c h ra m
m a t r ix m o d if ie r
P d P d -M g M g P O 4 M g -P O 4
5 g P d + 3 g M g
a d 2 0 l s a m p le
D 2 - b a c k g r o u n d - c o r r e c t io n
b e tte r th a n
h ig h c u r r e n t p u ls e t e c h n iq u e
L O D ( liq u id ) : 1 , 7 n g /m l
L O D ( s o lid ) : 1 9 , 1 m g /k g
N ie d e r r h e in
X - R a y f lu o r e s c e n c e s p e c t r o m e t r y X R F
U n iv e r s it y
J rg e n S c h ra m
x - r a y f lu o r e s c e n c e b y
f illin g t h e h o le
f r o m o u t e r s h e lls
x - ra y re m o v e s
e le c t r o n
f r o m in n e r s h e ll
se c o n d a r y ta r g e t
e n e r g y d is p e r s iv e
L i-d r ift
d e te k to r
(E D X R F )
bu e
t
y
ra
x
s a m p le
N ie d e r r h e in
X - R a y f lu o r e s c e n c e s p e c t r o m e t r y X R F
U n iv e r s it y
J rg e n S c h ra m
E D X - 7 2 0 H S , F a . S h im a d z u
m u f f le fu rn a c e :
s ta rt = 2 3 0 C ,
e v e ry 1 5 m in p lu s 1 5 C ,
s to p b y a c h ie v in g ~ 3 2 0 C
N ie d e r r h e in
X R F - c a lib r a t io n
U n iv e r s it y
J rg e n S c h ra m
S ta n d a rd s u p p o rte d
fu n d a m e n ta l p a ra m e te r m e th o d
In te n s ity [c p s /u A ] S b K a lib r a tio n s k u r v e R 2

= 0 , 9 3 5 1
0 ,1 0 0 0 0 0
0 ,0 8 0 0 0 0 = > c a lib r a t e d w it h
0 ,0 6 0 0 0 0 w e lld e f in e d
0 ,0 4 0 0 0 0 P E a n d P E T
0 ,0 2 0 0 0 0
s ta n d a rd s
0 ,0 0 0 0 0 0
0 1 0 0 2 0 0 3 0 0 4 0 0 5 0 0 6 0 0 7 0 0 8 0 0 9 0 0 1 0 0 0
-0 ,0 2 0 0 0 0
S ta n d a r d V a lu e [m g /k g ]
N ie d e r r h e in
C o r r e la t io n G F A A S v s X R F
U n iv e r s it y
J rg e n S c h ra m
3 3 0
y = 1 ,6 7 1 5 x - 1 3 4 ,1 9
R 2 = 0 ,9 9 9 9
3 1 0
(a n tim o n y in g /g ) _
2 9 0
2 7 0
g
x
R F A - 1 3 4 ,2
g
x = x =
R F A
2 5 0 d e p e n d a b le A A S
g / g
1 ,6 7 1 5
g / g
2 3 0
2 2 0 2 3 0 2 4 0 2 5 0 2 6 0 2 7 0 2 8 0
A A S (a n tim o n y in g /g )
N ie d e r r h e in
E x t r a c t io n w it h a q u e o u s f o o d a d d it iv e s
U n iv e r s it y
J rg e n S c h ra m
1 5 P E T b o t t le s o n t u r n t a b le
c (S
5 0 b ) 0 i n m d i f f l e rP e E n t T - b o t t le s
s o lu tio n s
E 5U 0 S b m l i m l i t o v f a l um e o d e l s o lu t io n
1 0
5 6 h le a c h in g / e x t r a c t io n
2 4 h s t o r in g a t 7 0 C
c (S b ) [n g /g ]
E U - S b - lim it = 5 g /l
5
4 ,5 7 0 5 4 3 7 6 3 3 ,5 2 8 6 8 8 1 2 3 ,7 1 4 1 3 1 9 7 4 5 ,7 0 5 3 6 7 0 7 1 2 ,8 0 6 1 8 7 7 8 1 5 ,9 7 4 2 6 0 0 2 7 1 3
0
/l
r
id
3
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id
id
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N ie d e r r h e in
E x t r a c t io n w it h a q u e o u s f o o d a d d it iv e s
U n iv e r s it y
J rg e n S c h ra m
E x t r a c t in g o f a n t im o n y f r o m 5 0 0 m l P E T - b o t t le s
w it h 5 0 m l 6 , 4 m m o l/ l p h o s p h o r o u s a c id
a t 7 0 C s to ra g e
1 5
c (S b ) y = 0 ,1 4 1 2 x - 0 ,0 4 2 2
E U S b lim it v a lu e 2
R = 0 ,9 9 0 6
1 0
c (S b ) [n g /g ]
5
0
0 2 0 4 0 6 0 8 0 1 0 0
tim e [h ]
N ie d e r r h e in
P o s p h a t e s in C o la - s o f t d r in k s
U n iv e r s it y
J rg e n S c h ra m
c a p illa r y
D e t e r m in a t io n : U V / V is - D e t e c t o r
C a p illa r y e le c t r o p h o r e s is D A D
e le k t r o d e s
e le k t r o ly t e
h ig h v o lt a g e
2 0 - 4 0 0 0 0 V
T y p e ID c (H 3 P O 4 ) [m m o l/l]
T o p s ta r , T r in k g u t T S 4 ,7
C o c a - C o la C C 5 ,0
P e p s i- C o la P C 5 ,0
F re e w a y , L ID L F W 5 ,2
A fr i- C o la A C 9 ,1
N ie d e r r h e in
A n t im o n y in C o la - s o f t d r in k s
U n iv e r s it y
J rg e n S c h ra m
B o t t le s : S t a r t in g c o n c e n t r a t io n o f
a n t im o n y a f t e r b u y in g t h e s a m p le s
7 ,0 1 0
6 ,0 9
5 ,0
D r in k in g w a t e r lim it f o r 8
c (H 3 P O 4 ) [m m o l/l]
a n t im o n y in t h e E U = 5 g / l.
c (S b ) [n g /g ]
4 ,0 7
3 ,0 6
2 ,0 5
1 ,0 4
0 ,0 3
D e s t. W a s s e r T S C C P C F W A C
N ie d e r r h e in
U n iv e r s it y
J rg e n S c h ra m
7 1 0
B o t t le s : C o n c e n t r a t io n o f
a n t i m c ( o S b n ) w y i t h f u a r t h f e rt c e o n r t a c 3 t t o 9 P E T d - b o a t t l e y s s o n t u r n t a b l e
c ( S b ) s ta r tin g c o n c e n tr a tio n
6 9
c (H 3 P O 4 )
5 0 m E U S l b c l i m oi t v a l la u e i n 5 0 0 m l b o t t l e a t R T
5 8
c (H 3 P O 4 ) [m m o l/l]
c (S b ) [n g /g ]
4 7
s ta rt-c o n c .
3
e n d -c o n c . 6
2 5
1 4
0 3
d e s t. W a te r T S C C P C F W A C
N ie d e r r h e in
U n iv e r s it y
J rg e n S c h ra m
E x tr a c tin g P E T -g r a n u la te
- r o ta tin g in H D P E - b o ttle s ( S b fre e )

fo r 3 9 d a y s
- 1 0 0 m l b o ttle s
- 2 5 m l d iffe r e n t C o la ty p e s
- 5 g g r a n u la te ( c e r t if ic a t e d b y a n C o la - p r o d u c e r )
T h e s u r fa c e o f th e g r a n u la te is 8 tim e s s m a lle r ,
th a n th a t o f a n 5 0 0 m l b o ttle !!
N ie d e r r h e in
U n iv e r s it y
J rg e n S c h ra m
G r a n u la t e s : C o n c e n t r a t io n o f a n t im o n y
a f t e r cc (( 3 SH b3 9 )P w O i 4t h d ) f u ar t h e y r c s o n t oa c t n t o P Et Tu - g r r a n n u t l a a t e b l e 5 0 m l c o l a
3 5 1 0
E U S b l i m i n i t v a 5l u e 0 0 m l b o t t le a t R T
9
3 0
8
2 5 7
c (H 3 P O 4 ) [m m o l/l]
c (S b ) [n g /g ]
6
2 0
5
1 5
4
1 0 3
2
5
1
0 0
d e s t. w a te r T S C C P C F W A C
N ie d e r r h e in
P E T - b o t t le v s . P E T - g r a n u la t e
U n iv e r s it y
J rg e n S c h ra m
n o r m a t io n o f : - s u rfa c e (c o n ta c t a re a )
- e lu t io n t im e
- e lu t io n v o lu m e
2
( S b e lu a t ) c e lu a t - c s ta r t - 1 - 1
E S b / P E T = = [n g d c m ]
(t) ( A ) V s a m p le t e lu a t A P E T
N ie d e r r h e in
U n iv e r s it y
J rg e n S c h ra m
g r a n u la t e s
b o t t le s
N ie d e r r h e in
P r o d u c t io n o f P E T - b o t t le s
U n iv e r s it y
J rg e n S c h ra m
N ie d e r r h e in
U n iv e r s it y
J rg e n S c h ra m
2 m m
S t r e c h in g o f t h e m a t e r ia l d u r in g b o t t le p r o d u c t io n
m in im iz e s r is k o f le a c h in g a n t im o n y .
= > m o r e c r y s t a liz e d r e g io n s in p o ly m e r
N ie d e r r h e in
R is k o f C o la in P E T - b o t t le s ? ? ? ? ?
U n iv e r s it y
J rg e n S c h ra m
A t R T b o t t le w ill r e a c h E U - lim it
n o t b e fo re 4 y e a rs
-
b u t t h e p o s s ib le c a n c e r o g e n it y
m a k e s it v e r y r is k y !
N ie d e r r h e in
S u m m a ry
U n iv e r s it y
J rg e n S c h ra m
A n t im o n y in P E T - m a t e r ia l
- V a lid a t e d q u a n t if ic a t io n w it h G F A A S p o s s ib le
- R F A c a n b e c a lib r a t e d w it h r e s u lt s o f G F A A S
A n t im o n y le a c h in g e x p e r im e n t s
- S b w ill b e le a c h e d u n d e r n o r m a l c o n d it io n s
- s ig n if ic a n t S b - c o n c . in c o la s o f t d r in k s
( d u e t o p r o d u c t io n ? ) ( u p t o 5 , 4 0 , 5 g / l)
- a t R T b o t t le w ill r e a c h E U - lim it n o t b e f o r e 4 y e a r s
- p o s s ib le c a n c e r o g e n it y is v e r y r is k y
T Y
N
ie d e r r h e in
H A N K O U
U n iv e r s it y
I n s tr u m e n te lle u n d U m w e lts c h u tz a n a ly tik
J rg e n S c h ra m
fo r
Y o u r
a tte n tio n
T h is w o r k w a s g e n e r o u s ly
su p p o rte d b y :
H o c h s c h u le
N ie d e r r h e in
N ie d e r r h e in U n iv e r s ity
o f A p p lie d S c ie n c e s

The Plastic Planet: Antimony in PET - Bottles

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The Plastic Planet: Antimony in PET - Bottles

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N ie d e r r h e in

In te n s ity [c p s /u A ] S b K a lib r a tio n s k u r v e R 2

- r o ta tin g in H D P E - b o ttle s ( S b fre e )

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