1
De e mina ion he se -o mig a ion o ink in ca dboa d-
cups used in co ee ending machines
Es he Asensio, Te esa Pei o and C is ina Ne ín*
Depa men o Analy ical Chemis y, A agon Ins i u e o Enginee ing
Resea ch I3A, CPS-Uni e si y o Za agoza, To es Que edo Building,
Ma ía de Luna 3, 50018 Za agoza, Spain.
*Co esponding au ho : Tel: +34 976761873, ax: +34 976762388. E-
mail add ess: cne in@uniza .es
E-mail add ess: (Es he Asensio) es he ac@uniza .es and (Te esa
Pei o) 701586@uniza .es
Manusc ip Ti le Page
Highligh s
- A p ocedu e o he analysis o mig an s by HS-SPME-GC-MS o he
analysis o ca dboa d-cups as ood con ac ma e ial has been
op imized.
- Mig a ion es s wi h simulan C (20% E OH) and D1 (50% E OH) we e
ca ied ou .
- The use o p in ed ca dboa d-cups wi h he selec ed be e ages can
be conside ed app op ia e.
- Mig an compounds om ca dboa d-cups (ink, pulp wood and LDPE
coa ing) ha e been iden i ied and quan i ied
Highligh s ( o e iew)
ink
ca dboa d
LDPE
Food con ac
ma e ial
(ink ans e ence o
inne side)
Mig a ion o
be e age
(co e)
Regula ion (EU) No.
10/2011
Simulan C
Simulan D1
Sc eening o
ola ile compounds
in ca dboa d-cups
Mig a ion s udy
G aphical Abs ac s
1
De e mina ion he se -o mig a ion o ink in ca dboa d-
cups used in co ee ending machines
Es he Asensio, Te esa Pei o and C is ina Ne ín*
Abs ac
The se -o mig a ion om p in ing inks can cause al e a ions in
he sa e y and accep abili y o ood. The e o e, i s con ol in he
ood indus y is o special impo ance. The aim o his s udy was
he de e mina ion o he mig a ion o compounds coming om
di e en ypes o ca dboa d-cups used in co ee ending machines.
The ola ile compounds p esen in ca dboa d-cups we e s udied and
speci ic mig a ion s udies we e ca ied ou by solid phase
mic oex ac ion wi h headspace coupled o gas ch oma og aphy (HS-
SPME-GC-MS). The mig a ion o compounds om he ca dboa d-cups
manu ac u ing ma e ial, plas ic coa ing (LDPE) and p in ing inks
we e iden i ied and quan i ied. Those mig an s lis ed in he
Regula ion No. 10/2011 p esen ed alues lowe han he speci ic
mig a ion limi (SML), al hough a se ies o non-lis ed and non-
au ho ized compounds we e iden i ied. F om he esul s ob ained he
isk assessmen o he ending cups om wo di e en companies
has been done.
*Abs ac
1
De e mina ion he se -o mig a ion o ink in ca dboa d-
cups used in co ee ending machines
Es he Asensio, Te esa Pei o and C is ina Ne ín*
Depa men o Analy ical Chemis y, A agon Ins i u e o Enginee ing
Resea ch I3A, CPS-Uni e si y o Za agoza, To es Que edo Building,
Ma ía de Luna 3, 50018 Za agoza, Spain.
*Co esponding au ho : Tel: +34 976761873, ax: +34 976762388. E-
mail add ess: cne in@uniza .es
E-mail add ess: (Es he Asensio) es he ac@uniza .es and (Te esa
Pei o) 701586@uniza .es
Abs ac
The se -o mig a ion om p in ing inks can cause al e a ions in
he sa e y and accep abili y o ood. The e o e, i s con ol in he
ood indus y is o special impo ance. The aim o his s udy was
he de e mina ion o he mig a ion o compounds coming om
di e en ypes o ca dboa d-cups used in co ee ending machines.
The ola ile compounds p esen in ca dboa d-cups we e s udied and
speci ic mig a ion s udies we e ca ied ou by solid phase
mic oex ac ion wi h headspace coupled o gas ch oma og aphy (HS-
SPME-GC-MS). The mig a ion o compounds om he ca dboa d-cups
manu ac u ing ma e ial, plas ic coa ing (LDPE) and p in ing inks
we e iden i ied and quan i ied. Those mig an s lis ed in he
Regula ion No. 10/2011 p esen ed alues lowe han he speci ic
mig a ion limi (SML), al hough a se ies o non-lis ed and non-
au ho ized compounds we e iden i ied. F om he esul s ob ained he
isk assessmen o he ending cups om wo di e en companies
has been done.
Keywo ds: ca dboa d, ood con ac , p in ing inks, isk assessmen ,
se -o mig a ion, ending cups, NIAS, mig a ion.
*Manusc ip showing all ack changes
3
1. In oduc ion
Food and be e ages may in e ac s ongly wi h he ma e ials ha
hey ouch and his is specially impo an in ending machines,
whe e o en he con ac is a high empe a u e. These in e ac ions
may esul in mig a ion o subs ances om he ood con ac
ma e ials o he be e ages, a ec ing bo h he odou , quali y o
ood as well as he heal h o consume s (Azna e al., 2015, 2016;
Clemen e e al., 2016; Domeño e al., 2017).
The consump ion o ho d inks (co ee, co ee wi h milk, e c.) om
ending machines has become a common p ac ice in he wo kplace and
leisu e. Al hough he po en ial mig a ion is e y high wi h he
ma e ials cu en ly used in ending machines, e y ew s udies ha e
been pe o med o demons a e he sa e y in use o hese ma e ials.
In his ype o machines, he cups, usually made o ca dboa d wi h
a plas ic coa ing and p in ed on he ou side, a e s acked inside
he dispensing machine un il he cus ome buys he p oduc . Se -o
mig a ion can occu when he ca ons a e s o ed in olls, o when
he pape cups a e s acked one inside he o he . In hese
condi ions, he se -o phenomena causes he mig a ion o compounds
om he con aine i sel o he p oduc , ha is, o he ho
be e age.
P in ing inks a e mix u es o chemical compounds, usually applied
on he ou e side o FCM (Food Con ac Ma e ial). Among hem,
ul a iole (UV) cu able inks a e mix u es made o esins o
oligome s, pigmen s, addi i es, monome s and pho oini ia o s, which
a e esponsible o abso bing he UV ene gy, o ming eac i e
species capable o ini ia ing a chain eac ion (Lago a al., 2015;
B ionisio-Lemos e al., 2017). The p esence o p in ing ink
componen s coming om ood packaging in o ood is a subjec o
4
conce n, ha caused a Rapid Ale Sys em o Food and Feed (RASFF)
in Sep embe 2005, when 2-isop opyl hioxan hone (ITX), a
pho oini ia o p esen in UV-cu ed inks, was de ec ed in baby milk
(RASFF, 2005).
Pape and ca dboa d a e po ous ma e ials, whe e chemicals can
mig a e om he ou side h ough he packaging. P in ing inks ha e
been shown o mig a e h ough pape and ca dboa d o d y and liquid
oods simulan s (Suciu e al., 2013; Cai e al., 2017; Rosenmai e
al., 2017). The la ge po e size o he pape -de i ed ma e ials
allows he mig a ion o he smalle molecules om he ou side o
he inside o he ood. The use o ba ie ma e ials can
signi ican ly educe ood con amina ion by di ec ans e ence, bu
he se -o phenomena s ill emains.
As ood con ac ma e ials, pape & boa d a e no ha monized in
Eu opean legisla ion. The esolu ion app o ed by he Council o
Eu ope es ablished he ules o apply o pape and boa d o ood
con ac (RESAP, 2005), bu he gene al equi emen s es ablished by
he ame Regula ion (EC) 1935/2004 apply o any FCM: hey should
no ans e hei cons i uen o oods u s in quan i ies ha
could endange human heal h o b ing abou an unaccep able change
in he composi ion o he oods u s o a de e io a ion in he
senso y cha ac e is ics. In o he wo ds, mig a ion o po en ial
ha m ul o de imen al subs ances om pape in o oods should be
a oided o below limi s o conce n (Guazzo i e al., 2015).
I has been demons a ed ha no only in en ionally added
compounds, such as monome s, an ioxidan s o plas icize s, mig a e
o ood bu also non-in en ionally added subs ances (NIAS) ha can
a ise om di e en o igins (Azna e al., 2012; Ne ín e al.,
2013). The e o e, he analysis ha allows he iden i ica ion o
5
NIAS is as impo an as he pe o mance o a a ge analysis o he
known addi i es. The e o e, i s con ol in he ood indus y
h ough global and speci ic mig a ion s udies is o special
impo ance.
Mig a ion s udies and se -o de e mina ion om p in ing inks
equi e sensi i e analy ical p ocedu es o iden i y e e y single
compound coming om he ma e ial. Fo ola ile subs ances, GC-MS
is he mos used echnique, al hough he combina ion wi h SPME
would be o en needed o enhance he sensi i i y (Pe e s e al.,
2019). The aim o his wo k is o s udy he mig a ion o compounds
coming om di e en ypes o ca dboa d-cups used in co ee
ending machines. In o de o ul ill his objec i e, mig a ion
s udies we e done. Subsequen ly, speci ic mig a ion analysis we e
ca ied ou by SPME-GC-MS. Then, he ola ile compounds coming om
he cups we e iden i ied and he pa e n ecogni ion was done,
iden i ying hose coming om se -o o p in ing inks. F om he
esul s ob ained isk assessmen o he ending cups was done.
2. Ma e ial and me hods
2.1. Chemicals and analy ical s anda ds
Analy ical s anda ds used o quan i ica ion we e bough in Sigma-
Ald ich (Ba celona, Spain): 2,6-di e -bu ylcyclohexa-2,5-diene-
1,4-dione (CAS 719-22-2); 3,5-di e -bu yl-4-hyd oxy benzaldehyde
(CAS 1620-98-0); 2,6-di(p opan-2-yl)naph halene (CAS 24157-81-1),
ibu yl 2-hyd oxyp opane-1,2,3- ica boxyla e (CAS 77-94-1),
me hyl hexadecanoa e (CAS 112-39-0); 2,6-di e -bu yl-4-
me hylphenol (CAS 128-37-0); 1-hexadecanol (CAS 29354-98-1);
ibu yl ace ylci a e (CAS 77-90-7); alpha-me hyls y ene (CAS 98-
83-9); 2-e hyl,1-hexanol (CAS 104-76-7) and benzophenone as
6
in e nal s anda d(CAS 119-61-9). E hanol was pu chased om
Scha lab (Mad id, Spain) and sodium chlo ide om Pan eac
(Ba celona, Spain).
All s ocks solu ions o he analy ical s anda ds we e p epa ed a a
concen a ion o 1000 µg/g in e hanol. The wo king solu ions o all
he compounds we e dilu ed o 20% e hanol. 10 µL o an in e nal
s anda d solu ion (1000 µg/g) we e added o all wo king solu ions
and samples. All solu ions and calib an s we e unde g a ime ic
con ol.
2.2. Samples
Fo he de elopmen o his s udy, wo di e en ypes o
ca dboa d-cups we e selec ed, p o ided by wo di e en companies
ha o e ho be e ages in ending machines. Th oughou he wo k,
e e ence will be made o ype A cups (company 1) and ype B cups
(company 2). Bo h ypes o cups a e made o ca dboa d wi h he
ou e -side p in ed wi h he company's d awings and co e ed inside
by a plas ic ilm: Low-Densi y Polye hylene (LDPE), indispensable
o i s ood use.
2.3. Sc eening o ola ile compounds in ca dboa d-cups by HS-SPME-
GG-MS
Be o e he speci ic mig a ion es s, he ola ile compounds p esen
in he ca dboa d-cups we e analyzed. Canellas e al. (2016) and
Domeño e al. (2017) used SPME coupled o GC-MS ei he by head-
space (HS) o by di ec imme sion o iden i y ola ile compounds in
plas ic packaging ma e ials, espec i ely. Simila p ocedu e was
a emp ed he e.
13
packages wi h an aluminum ba ie laye and polye hylene ood
con ac laye . The compounds benzene, 1,1´-(1,2-
cyclobu anediyl)bis-,cis- (deg ada ion om an ioxidan –class III),
me hyl palmi a e (monome ) in ood con ac side; 2,4-di- e -
bu ylphenol (an ioxidan deg ada ion compound); naph halene,
1,2,3,4- e ahyd o-1-phenyl (co-monome –class III); hexadecanoic
acid (deg ada ion om slip agen ); oc adecanoic acid (monome /slip
agen ) and me hyl dehyd oabie a e ( om pape ) we e iden i ied in
bo h p in ed-side and ood con ac side. Also he p esence o
ans-1,2-diphenyl cyclobu ane (monome byp oduc –class III), ha
in his s udy was iden i ied in samples A wi h simulan D1, was
a ibu ed o se -o mig a ion.
In samples A and B wi h simulan D1 dehyd oabie ic acid (DHAA) was
iden i ied. Ce ain FCMs ha e been epo ed o con ain DHAA and
abie ic acid (AA), which can mig a e o ood simulan s om pape
and boa d packaging (Ozaki e al., 2006; Webe e al., 2006;
Rosenmai e al., 2017).
The s udy ca ied ou by Clemen e e al. (2016) showed he p esence
o ibu yl aconi a e (0.287 – 0.395 mg/kg) and 3,5-di- e -bu yl-
4-hyd oxybenzaldehyde (0.086 – 0.192 mg/kg) in simulan D1 only in
p in ed mul ilaye (PE/Al/PP/ink), ela ing hei p esence wi h a
possible se -o mig a ion. In his s udy he i s compound was
ound in highe concen a ion (0.978 mg/kg) om sample B in
simulan D1, con i ming ha he sou ce was he p in ing ink.
A se ies o compounds classi ied as class II acco ding o he
C ame ules we e iden i ied in bo h samples wi h simulan D1, such
as me hyl-2-hyd oxy-hep adecanoa e and 6,10,14- ime hylpen adecan-
2-one. In sample A wi h bo h simulan s he 4-phenylaze idin-2-one
classi ied as class III was iden i ied. The ollowing compounds
14
we e iden i ied in simulan D1 om sample A: 3-me hyl-3-phenyl
aze idine, 5-me hyl-5-(4,8,12- ime hyl idecyl)oxolan-2-one and
1,2-diphenyl p op-2-en-1-one, all o hem classi ied as class III.
Among he o he compounds iden i ied in mig a ion es s pima al and
pima ic acid, classi ied as class III espec i ely, we e ela ed
wi h he manu ac u ing o he ca dboa d-cups (wood/pape ). The
p esence o 2,6-diisop opyl naph halene (class III) could be
ela ed wi h ecycled pape /ca dboa d used in he manu ac u ing o
ca dboa d-cups (Webe e al., 2004; Ne ín & Asensio, 2004, 2007;
Asensio & Ne ín, 2009).
4. Conclusions
A e ca ying ou he speci ic mig a ion analysis o cups used in
ending machines, using he app op ia e simulan s acco ding o he
in ended use and unde he es condi ions se by Regula ion (EU)
No. 10/2011, he alues ob ained did no exceed he limi s
es ablished by he legisla ion (SML). The e o e, he use o p in ed
ca dboa d-cups wi h he selec ed be e ages “gou me long co ee”
and “gou me co ee la e" can be conside ed app op ia e.
Howe e , i is impo an o highligh he p esence o compounds
om bo h he ma e ial o he ca dboa d-cups (wood pulp) and he
plas ic coa ing (LDPE). Se e al compounds classi ied as Class II
and Class III acco ding o he C ame ules, s and ou he
impo ance o he s udy and he equi ed con ol o hem, while
hei analysis sugges s ha his ood con ac ma e ial is unlikely
o con ibu e signi ican ly o die a y C ame - h eshold exceedance.
F om he s udy ca ied ou we can conclude ha he se -o o
p in ing inks is a eali y and an impo an sou ce o mig an s in
co ee ca dboa d-cups used in ending machines. Some o he
15
compounds ound a e no au ho ized o building ood packaging
ma e ials. E en hough hey a e coming om p in ing inks, he
con ac laye in he cups is LDPE, wha makes his s uc u e as a
mul ilaye and hen, included in he egula ion 10/2011/EU. I is
well known ha di usion o low pola o ganic molecules in LDPE is
e y as and consequen ly he so p ed compounds in di ec con ac
wi h LDPE can be easily ans e ed o he ood.
Acknowledgemen s
The au ho s acknowledge he unding p o ided by he Gobie no de
A agón (Spain) o he GUIA g oup [ inanciación g upo GUIA T53-17R].
16
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Webe , A., onW igh , A., Honkalampi-H€am€al€ainen, U., J€a inen,
M., Lhugueno , J.C., Se e in, I., Dahbi, L., S amma i, A., Zucco,
F., Tu co, L., Dahlman, O., Be aud, F., M€aki-Paakkanen, J.,
Hakulinen, P., Cas le, L., B adley, E., Salkinoja-Salonen, M.,
Ande sson, M., Hoo ns a, D., Renn, O., Schweize , P.J., 2006.
Biosa epape - Applica ion o Bioassays o Sa e y Assessmen o
Pape and Boa d o Food Con ac .
Table 1. Compounds iden i ied and en a i ely iden i ied by HS-SPME-GC-MS (HP-5MS) in ca dboa d-cups wi h he le el o oxici y
(TTC) acco ding o C amme classi ica ion and NOAEL alues.
Compounds
RT
(min)
CAS numbe
SML
(mg/kg)
NOAEL
(mg/kg bw/d)
C ame
Samples
SPME- ibe s
DVB/CAR/PDMS
PDMS
PA
Dodecane
8.16
112-40-3
NL
>1000
A
-
-
Undecane
9.38
1120-21-4
NL
>1000
A
-
-
Nonanal
9.63
124-19-6
NL
I
A
-
-
-me hyls y eneb
10.50
98-83-9
0.05
A
-
-
2-e hyl-1-hexanolb
11.40
104-76-7
30
A
-
-
T idecane
12.70
629-50-5
NL
I
A
-
-
Longicyclene
13.74
1137-12-8
NL
I
A
A
-
Isolongi olene
14.00
1135-66-6
NL
I
A
A
-
Te adecane
14.08
629-59-4
NL
I
A
-
-
Longi olene
14.22
475-20-7
NL
I
A,B
A,B
-
2,6-di- e -bu yl-4-hyd oxy-4-me hyl-2,5-
cyclohexadien-1-one
14.88
10396-80-2
NL
III
A,B
-
-
Bu ylhyd oxy olueneb
18.72
128-37-0
3
A,B
A,B
A
3,5-di- e -bu yl-4-hyd oxybenzaldehydeb
21.48
1620-98-0
NL
II
-
-
A
Naph halene,1,2,3,4- e ahyd o-1-phenyl
22.99
3018-20-0
NL
III
-
-
A
Ph halic acid,hep -4-yl isobu yl es e
23.46
NIST356783
NL
I
-
-
A
1-hexadecanolb
23.17
36653-82-4
_c
-
-
B
Benzoic acid, 4-( ans-4-bu ylcyclohexyl)-
,4-bu oxy-2,3-dicyanophenyl es e
24.24
75941-90-1
NL
-
A,B
A,B
Isoph halic acid, di(2- luo o phenyl)es e
24.41
NIST
344664
NL
III
-
A
-
Me hyl s ea a e
24.94
112-61-8
NL
1390
-
-
A
Ace yl ibu yl ci a eb
26.27
77-90-7
32a
-
-
B
Ph halic acid, di(2-p opylpen yl)es e
28.26
70910-37-1
NL
I
-
-
A,B
Bis(2-e hylhexyl) ph hala e
28.28
117-81-7
1.5
-
B
-
NL no lis ed in Regula ion 10/2011; aSML (T) (g oup es ic ion); bCon i med wi h s anda ds; cSpeci ic mig a ion limi o 60
mg/kg (subs ance o which no speci ic mig a ion limi by Regula ion 10/2011).
Table
Table 2. Compounds iden i ied and en a i ely iden i ied by HS-SPME-GC-MS (BP-20) in ca dboa d-cups wi h he le el o oxici y
(TTC) acco ding o C amme classi ica ion and NOAEL alues.
Compounds
RT
(min)
CAS numbe
SML
(mg/kg)
NOAEL
(mg/kg bw/d)
C ame
Samples
SPME- ibe s
DVB/CAR/PDMS
PDMS
PA
2-p openal
2.31
107-02-8
NL
0.05
-
-
A
Bu ane-1,2-diol
7.07
584-03-2
NL
200
B
B
-
1,3-dioxolane
8.25
646-06-0
5
B
-
-
S y ene
8.67
100-42-5
_c
-
-
A
2-me hylsul onyl ace oni ile
7.77
2274-42-2
NL
III
-
-
A
Dodecane
8.29
112-40-3
NL
>1000
A
-
-
Cyclooc a e aene
8.92
629-20-9
NL
I
A
-
-
-me hyls y eneb
10.25
98-83-9
0.05
A
-
A
2-e hyl-1-hexanolb
12.33
104-76-7
30
A
-
A
Fu u al
12.63
98-01-1
NL
36
A
-
-
Longicyclene
12.94
1137-12-8
NL
I
-
A
-
Benzaldehyde
13.15
100-52-7
_c
A,B
-
-
Isolongi olene
13.28
1135-66-6
NL
I
A
A
Longi olene
13.87
475-20-7
NL
I
A,B
A
A
2-(2-e hoxye hoxy) e hanol
14.49
111-90-0
3a
I
A
-
-
Ace ophenone
14,83
98-86-2
NL
75
A,B
-
-
1-decanol
16.05
112-30-1
_c
A
-
A
Bu ylhyd oxy olueneb
17.60
128-37-0
3
A
A,B
A
1-bu yl-4-[2-(4-e hylphenyl)e hylnyl] benzene
18.11
117392-63-9
NL
III
-
A
-
Phenol
18.53
108-95-2
_c
A,B
-
-
Isop opyl my is a e
19.03
110-27-0
NL
I
-
A,B
-
Isoph halaldehyde
19.88
626-19-7
NL
I
A
-
-
3-me hyl-4-iso p opylphenol
20.53
3228-02-2
NL
I
-
A
-
1-(3-e hylphenyl) e hanone
20.87
22699-70-3
NL
I
A,B
-
-
7-ace yl-6-e hyl-1,1,4,4- e ame hyl e alin
21.96
88-29-9
NL
3
A,B
A,B
-
3,5-di- e -bu yl-4-hyd oxybenzaldehydeb
22.37
1620-98-0
NL
II
A
-
-
Hexadecen-1-ol, ans-9
22.59
64437-47-4
NL
I
-
B
-
Naph halene,1,2,3,4- e ahyd o-1-phenyl
23.16
3018-20-0
NL
III
-
-
A
Ph halic acid,hep -4-yl isobu yl es e
23.49
NIST356783
NL
I
-
B
-
Benzoic acid
23.36
65-85-0
_c
A,B
-
-
1-hexadecanolb
23.58
36653-82-4
_c
B
-
-
Table
Isoph halic acid, di(2- luo o phenyl)es e
24.25
NIST
344664
NL
III
B
-
-
NL no lis ed in Regula ion 10/2011; aSML (T) (g oup es ic ion) by Regula ion 10/2011 ; bCon i med wi h s anda ds; cWi hou
Speci ic mig a ion limi (60 mg/kg as global mig a ion limi is applied).
