Food Packaging and Shel Li e 40 (2023) 101183
A ailable online 19 Sep embe 2023
2214-2894/© 2023 The Au ho s. Published by Else ie L d. This is an open access a icle unde he CC BY-NC-ND license (h p://c ea i ecommons.o g/licenses/by-
nc-nd/4.0/).
In es iga ion o mig an s om can coa ings: Occu ence in canned
oods u s and exposu e assessmen
P. V´
azquez-Lou ei o
a
, A. Les ido-Ca dama
a
, R. Send´
on
a
, J. Bus os
b
, R. Ca iou
c
, P. Pasei o-
Losada
a
, A. Rod íguez-Be naldo de Qui ´
os
a
,
*
a
Depa men o Analy ical Chemis y, Nu i ion and Food Science, Facul y o Pha macy, Uni e si y o San iago de Compos ela, 15782 San iago de Compos ela, Spain
b
Na ional Food Cen e, Spanish Agency o Food Sa e y and Nu i ion, E-28220 Majadahonda, Spain
c
Oni is, INRAE, LABERCA, F-44300 Nan es, F ance
ARTICLE INFO
Keywo ds:
Polyme ic can coa ings
Epoxy
Polyes e
Monome s
Oligome s
Exposu e assessmen
ABSTRACT
In he p esen s udy mig an s om can coa ings, speci ically epoxy and polyes e esins, we e de e mined in
canned oods. Ta ge ed and non- a ge ed app oaches we e applied o explo e he mig a ing compounds.
Bisphenol A (BPA), BADGE .2 H
2
O, BADGE⋅H
2
O.HCl and cyclodiBADGE om epoxy esins and h ee monome s i.
e., e eph halic acid (TPA), ph halic acid (PA), isoph halic acid (IPA) and ou en a i ely iden i ied oligome s
om polyes e esins we e ound in he oods u s. Using he consump ion da a om he Spanish consump ion
su ey, die a y exposu e o hese chemicals was assessed. Mainly, ou da a sugges ed low exposu e o he mi-
g an s e alua ed, howe e , i is impo an o highligh ha cyclic oligome s showed he highes mean exposu e
(0.00646–2.75
μ
g/kg bw/day) and hese molecules belong o C ame class III, which means ha hey may ha e
signi ican oxici y.
1. In oduc ion
The ood con ac su ace o me al cans is o en co e ed wi h poly-
me ic coa ings ha se e as a unc ional ba ie s be ween he ood and
he me allic can. Coa ings based on di e en chemis ies ha e been
applied. T adi ionally, BADGE epoxy esins ha e been ex ensi ely
employed owing o hei excep ional mechanical p ope ies and chem-
ical esis ance (LaKind, 2013). Al hough hey a e s ill used he e is a
g owing conce n abou he po en ially ad e se e ec s o BPA on con-
sume s’ heal h. In line wi h his, he ecen EFSA d a opinion p oposes
lowe ing he TDI down o 0.04 ng/kg bw/day (EFSA, 2021). This si u-
a ion has led o he de elopmen o new coa ings. Polyes e -based
coa ings appea as subs i u e o epoxy esins (D i ield e al. 2018).
Polyme ic coa ings a e mix u es ha con ain a wide a ie y o
compounds. Besides he in en ionally added subs ances (e.g., addi i es,
p epolyme s, monome s and so on) hey also con ain subs ances o med
du ing he p ocessing o he polyme ic ma e ials, (e.g., eac ion p od-
uc s, oligome s, and so on). All hese subs ances may mig a e in o he
ood. Mos o hem a e unknown and hei oxici y has no been e alu-
a ed (G ob, Spinne , B unne & E e , 1999). In he case o oligome s,
hey could be conside ed subs ances inhe en o polyme s since hey a e
always p esen (Hoppe, de Voog , & F anz, 2016). Recen ly, he
mig a ion o oligome s om ood con ac ma e ials has ecei ed
inc easing conside a ion in he EFSA isk assessmen s (EFSA, 2016,
Tsocha zis, Lopes, Kappens ein, Tie z & Hoeks a, 2020).
To ensu e he p o ec ion o human heal h, polyme ic coa ings as all
ypes o ood con ac ma e ials mus comply wi h he equi emen s o
A icle 3 o he Regula ion (EC) No. 1935/2004 (Eu opean Union,
2004). A p esen , he e is no ha monized legisla ion o coa ings in he
Eu opean Union. The e is a Resolu ion o he Council o Eu ope ha
includes a gene al guideline and a echnical documen wi h he lis o
subs ances o be used in he manu ac u e o coa ings o ood con ac
(CoE, 2009).
Mig a ion da a oge he wi h ood consump ion a e key in o ma ion
o exposu e and sa e y e alua ions (Poças, & Hogg, 2007). The e o e, i
is essen ial o analyse he packed oods o know whe he unaccep able
amoun s o mig an s a e p esen in he ood. A his poin , i is impo an
o men ion ha o many mig an s (e.g., oligome s) he e a e no com-
me cial s anda ds a ailable, which hampe he mig a ion quan i ica-
ion. The e o e, al e na i e app oaches should be explo ed, he cus om
syn hesis o chemical mig an s could be an op ion o o e come his
incon enience.
* Co esponding au ho .
E-mail add ess: [email p o ec ed] (A. Rod íguez-Be naldo de Qui ´
os).
Con en s lis s a ailable a ScienceDi ec
Food Packaging and Shel Li e
jou nal homepage: www.else ie .com/loca e/ psl
h ps://doi.o g/10.1016/j. psl.2023.101183
Recei ed 23 Ma ch 2023; Recei ed in e ised o m 28 July 2023; Accep ed 14 Sep embe 2023
Food Packaging and Shel Li e 40 (2023) 101183
2
On he o he hand, mig a ion da a in ood is also needed o a mo e
ealis ic exposu e es ima ion.
Ve y ew mig a ion da a in ood, pa icula ly ega ding polyes e
mig an s, ha e been published (D i ield e al. 2018; Pasei o-Ce a o,
DeJage , & Begley, 2019; Ca iou e al. 2022), and he e is e en less
da a on exposu e o mig an s eleased om he coa ings o me al cans.
This s udy aimed o de e mine s a ing subs ances and oligome s
mig a ed om polyme ic coa ings, speci ically epoxy and polyes e
esins, in o canned oods u s. Samples we e collec ed in o de o co e
di e en ood ypes and o be ep esen a i e samples o canned oods
widely consumed in Eu ope. The polyme ic coa ings we e iden i ied by
FTIR, and ex ac ed o iden i y po en ial mig an s, ha would la e be
analysed in he packaged ood. The analyses we e achie ed h ough
non- a ge ed me hods o unknown compounds (e.g., oligome s) and
a ge me hodologies o in en ionally added subs ances (e.g., mono-
me s). Finally, he exposu e o chemicals mig a ed om polyme ic
coa ings was es ima ed in he Spanish adul popula ion, combining
mig a ion da a wi h consump ion da a ob ained om he na ional
consump ion su ey.
2. Ma e ials and me hods
2.1. Samples
A o al o wen y- wo canned oods u s o se e al b ands and
co e ing di e en ood ypes (e.g., ish, ege ables, legumes, e c.) we e
pu chased in a local supe ma ke in San iago de Compos ela (Spain).
Samples we e selec ed among he canned oods mos consumed by he
Eu opean popula ion acco ding o he EFSA comp ehensi e Eu opean
ood consump ion da abase (e.g., macke el, unas and simila , len ils
e c.) (EFSA, 2022). De ailed in o ma ion (e.g., a con en , pH) is lis ed
in Table 1. The pH o he ood samples was de e mined in a simila way
o ha desc ibed in a p e ious s udy (Les ido-Ca dama e al., 2021). The
alues p esen ed in Table 1 a e he a e age o wo measu emen s.
The polyme ic ood con ac coa ings we e iden i ied by FTIR, o ha
pu pose small pieces o he di e en pa s o he can (lid, body, base and
seam) we e cu and analysed. Resul s a e displayed in Table 1.
2.2. S anda ds and eagen s
Ace oni ile (ACN) HPLC and LC-MS g ade, me hanol (MeOH) HPLC
and LC-MS g ade, e ahyd o u an (THF) HPLC g ade, o mic acid
98%−100% LC-MS g ade and i luo oace ic acid (TFA) we e om
Me ck (Da ms ad , Ge many). Ul apu e wa e ( ype I) was ob ained
om an Au woma ic Plus pu i ica ion sys em (Wasse lab, Na a a,
Spain).
Comme cially a ailable QuEChERS ki s con aining 4 g magnesium
sulpha e, 1 g sodium chlo ide, 1 g sodium ci a e dihyd a e, 0.5 g sodium
hyd ogen ci a e sesquihyd a e we e pu chased om Agilen (San a
Cla a CA, USA).
Fo he quan i ica ion o bisphenols and BADGEs, analy ical s an-
da ds used in his s udy we e desc ibed elsewhe e (Les ido-Ca dama,
Send´
on, Bus os, San illana, Pasei o-Losada & Rod íguez-Be naldo de
Qui ´
os, 2019). Independen solu ions o each bisphenol and BADGEs
we e p epa ed in ACN a a concen a ion o 1000 mg/L. A solu ion o
200 mg/L o cyclo-di-BADGE was p epa ed in a mix u e o ACN:THF
(30:20, / ). An in e media e mix solu ion o all compounds a a con-
cen a ion o 10 mg/L and calib a ion solu ions we e p epa ed in ACN
by subsequen dilu ions.
Analy ical s anda ds o poly alen ca boxylic acids, ph halic acid
(PA)≥99.5%, isoph halic acid (IPA)≥97%, e eph halic acid (TPA)≥
98%, and 3,4,5,6-d
4
-ph halic acid (PAd4) we e p o ided by Sigma-
Ald ich (Schnelldo , Ge many). Single s ock solu ions o 50 mg/L o
each compound we e made in ACN, excep o TPA which was p epa ed
in MeOH. Wo king solu ions o all compounds we e p epa ed in ACN:
H
2
O (50:50, / ) by subsequen dilu ions om a single in e media e mix
Table 1
Samples desc ip ion and FTIR iden i ica ion o polyme ic coa ings.
Can
Code
Food ype pH Fa con en
(%)
Polyme ic coa ing
AC Ligh una in oli e oil 6.0 14 Lid: ac ylic base
Body: ac ylic base
BN Tuna in oli e oil 6.4
16 Lid: ac ylic base
Body: ac ylic base
CH S u ed squid in
sun lowe oil
6.5 9.8 Lid: ac ylic base
Body: ac ylic base
CTO Macke el ille s in oma o
sauce
5.8 5.7 * Lid: ac ylic base
Body: ac ylic base
CAG Macke el ille s in
sun lowe oil
6.1 13 * * Lid: ac ylic base
Body: ac ylic base
CAO Macke el ille s in oli e
oil
6.1 12 * * Lid: ac ylic base
Body: ac ylic base
SCA Sa dines in oli e oil 6.4 23 * Lid: polyes e
Body: polyes e
SCO Sa dines in oli e oil 6.4 32.2 * ;
15.3 * *
Lid: ac ylic base
Body: ac ylic base
LE Riojan len ils 5.6 8.0 Lid: polyes e
Body: polyes e
Base: polyes e
Seam: PET
AL Mea balls in sauce 5.4 6.0 Lid: polyes e
Body: epoxy
Base: epoxy
Seam: PET
RAV Egg a ioli wi h mea and
oma o sauce
4.6 2.5 Lid: polyes e
Body: epoxy
Base: epoxy
Seam: PET
PAT S ewed po a oes wi h
mea
5.3 1.5 Lid: polyes e
Body: polyes e -
polyu e hane
Base: polyes e -
polyu e hane
Seam: PET
LEV Len ils wi h ege ables 5.2 2.7 Lid: polyes e
Body: polyes e -
polyu e hane
Base: polyes e
Seam: PET
PM Bell peppe s 3.7 <0.5 Lid: polyes e
Body: epoxy
Base: epoxy
Seam: PET
GUIM G een peas 5.9 <0.5 Lid: polyes e
Body: epoxy
Base: epoxy
Seam: PET
TOE Whole peeled oma o 4.1 0.1 Lid: ac ylic base
Body: ac ylic base
Base: epoxy
Seam: PET
CHA Sliced mush oom 5.1 0.1 Lid: ac ylic base
Body: epoxy
Base: epoxy
Seam: PET
TOT 100% Na u al c ushed
oma o
4.1 0.1 Lid: ac ylic base
Body: ac ylic base
Base: epoxy
Seam: PET
GUIB G een peas 6.1 0.8 * * Lid: ac ylic base
Body: polyes e
Base: polyes e
Seam: PET
TOR Ghe kin, ca o , pink
onion and black oli e
3.4 2.7 Lid: ac ylic base
Body: ac ylic base
Base: epoxy
Seam: PET
JU B oad g een beans 5.0 0 Lid: polyes e
Body: ac ylic base
Base: epoxy
Seam: polyes e
ME Pickled mussel 4.4 8.4 * * Lid: epoxy
Body: epoxy
P. V´
azquez-Lou ei o e al.
Food Packaging and Shel Li e 40 (2023) 101183
3
solu ion o 10 mg/L and s o ed a 4ºC. Each wo king solu ion con ained
he co esponding amoun o in e nal s anda d (IS) o yield a inal
concen a ion o 5 mg/L.
Bisphenol A e hoxyla e dime hac yla e (bisEMA) was acqui ed om
Sigma-Ald ich (Schnelldo , Ge many).
Bis(2-hyd oxye hyl) e eph hala e (BHET) used as a e e ence s an-
da d o he semi-quan i ica ion o some o he en a i ely iden i ied
oligome s was pu chased om Sigma-Ald ich (Schnelldo , Ge many). A
solu ion o 1000 mg/L was made in ACN, and in e media e solu ions
we e p epa ed by subsequen dilu ions.
Oligoes e s based on IPA and neopen ylglycol (NPG), speci ically
2NPG+2iPA(L), 2NPG+2iPA(C), 4NPG+4iPA(C) and d4–2NPG+2iPA
(C) we e used o iden i ica ion and quan i ica ion pu poses and as in-
e nal s anda d, espec i ely. Rega ding d4- 2NPG+2iPA(C), he
ammonium adduc (m/z 490.2) was selec ed o he quan i ica ion, he
p o ona ed molecula ion (m/z 473.2) was also obse ed.
De ailed in o ma ion abou he syn hesis p ocedu e is desc ibed
elsewhe e (Ca iou e al. 2022). Single s ock solu ions o 200 mg/L we e
made in ACN and he wo king in e media e solu ions we e made by
subsequen dilu ions in ACN:H
2
O (20:80, / ) wi h he co esponding
amoun o IS o yield a inal concen a ion o 1 mg/L.
2.3. Ins umen a ion and analy ical condi ions
2.3.1. FTIR
The polyme ic coa ing o he in e nal side o he me allic cans (body,
base, lid and seam) was iden i ied using a FTIR spec ome e (FTIR
4700, Jasco, Tokyo, Japan) coupled o an ATR (a enua ed o al e lec-
ance, ATR-PRO-ONE) acqui ing in a ange be ween 4000 and 650
cm
−1
. Spec a Manage ( e sion 2) so wa e was used o he acquisi ion
o he in a ed spec a and KnowI All 17.4.135. B so wa e o he
iden i ica ion, compa ing he sample spec a ob ained wi h IR Spec al
Lib a ies o Polyme s & Rela ed Compounds (Bio-Rad Labo a o ies, Inc.
Philadelphia, PA, USA).
2.3.2. HPLC-FLD
The iden i ica ion and quan i ica ion o bisphenols and BADGEs
we e pe o med wi h a HPLC-FLD me hod. A de ailed desc ip ion o he
equipmen used is p esen ed in an ea lie wo k (Les ido-Ca dama e al.
2021). The ch oma og aphic sepa a ion was pe o med on a
e e sed-phase column Phenosphe e 80 A ODS (2) (150 mm ×4.6 mm
in e nal diame e , 3 µm pa icle size) he mos a ed a 25 ◦C. Mobile
phases we e wa e (A) and ACN (B) using a g adien elu ion me hod in
he ollowing condi ions: he mobile phase s a ed wi h 80%A and 20%B
o 2 min, eaching 50%B a minu e 15 and, ollowed by ano he
g adien up o 100%ACN a minu e 40 and hold o 5 min. Finally, he
ini ial condi ions we e esume a minu e 50 wi h 5 min o pos - ime o
cleaning and equilib a ion o he column. The injec ion olume was 10
µL, and he luo escence de ec o was se a λex 225 nm and λem 305
nm. Mo eo e , LC-MS/MS was used o con i ma ion. The mass spec-
ome y condi ions applied we e epo ed in an ea lie s udy (Les i-
do-Ca dama e al. 2019).
2.3.3. LC-MS/MS
An LC-MS/MS me hod was used o quan i y he ca boxylic acids. A
ull desc ip ion o he ins umen used is p o ided elsewhe e (Les ido--
Ca dama e al. 2021). The ch oma og aphic sepa a ion was ca ied ou
on a e e sed-phase column Gemini C18, 110 A, (150 ×3 mm wi h an
in e nal diame e o 5 µm), also used in he p e ious wo k (Les ido--
Ca dama, e al. 2022). The mobile phases used we e wa e (A) and ACN
(B) bo h wi h 0.1% o mic acid ( / ), using a low a e o 0.3 mL/min
and a g adien elu ion me hod. B ie ly, he me hod s a ed wi h 95%A
and 5%B, inc easing g adually he pe cen age o B un il 10% a minu e
5, hen un il 20%B a minu e 10 and hen un il 30%B a minu e 20.
Finally, a minu e 21 inc eased 100%ACN o 5 min and he g adien
e u ned o ini ial composi ion o 5 min mo e. The column empe a u e
and he injec ion olume we e 35 ◦C and 10 µL, espec i ely.
Mass spec ome ic condi ions we e op imized by di ec in usion o a
solu ion o 25 mg/L o each compound in nega i e ESI mode. A a ge ed
me hod was ca ied ou o he iden i ica ion and quan i ica ion o h ee
poly alen ca boxylic acid monome s: PA, IPA and TPA. MS da a we e
acqui ed in selec ed eac ion moni o ing (SRM) mode. The m/z selec ed
p ecu so ion was m/z 164.6 o PA, IPA and TPA; which was he mos
sensi i e ion in he Q1 mass spec a. Two SRM ansi ions we e moni-
o ed: m/z 164.6 >121.1 ansi ion used o quan i ica ion pu poses o
IPA and TPA and m/z 164.6 >77.2 o quan i ica ion o PA wi h a
collision ene gy o 16 and 19 V, espec i ely.
The in e nal s anda d (PAd4), p e iously in used in he condi ions
de ailed abo e, he SRM ansi ions o m/z 169.2 >81.2 ( ansi ion used
o quan i ica ion pu poses), and m/z 169.2 >125.1 ( ansi ion used o
iden i ica ion pu poses) we e moni o ed wi h a collision gas ene gy o
19 and 14 V, espec i ely.
In addi ion, a non- a ge ed analysis was ca ied ou wi h he aim o
en a i ely iden i y polyes e oligome s ollowing he me hodology
desc ibed ea lie (Les ido-Ca dama, e al. 2022). Acco ding o ou p e-
ious esul s only posi i e elec osp ay ioniza ion (ESI) mode was
selec ed o he analysis; ni ogen was used as he nebulize gas a a
p essu e o 35 psi and a gon was used as auxilia y gas a a p essu e o 10
psi. The sp ay ol age was main ained a −3000 V. The MS da a we e
acqui ed in ull scan mode using wo anges (100–500 m/z and
500–1000 m/z) o inc ease he sensi i i y. The empe a u es o apo -
ize and capilla y we e 340 and 350 ◦C, espec i ely.
Fo he semi-quan i ica ion o he en a i ely iden i ied oligome s,
BHET was used as a p oxy compound. A selec ed ion moni o ing (SIM)
me hod was applied, and m/z 255 >193.1 ansi ion was selec ed o
quan i ica ion pu poses.
Wi h espec o he syn hesised oligoes e s, 2NPG+2iPA(L), 2NPG+
2iPA(C) and 4NPG+4iPA(C) we e injec ed unde he same condi ions,
and d4–2NPG+2iPA(C) was used as in e nal s anda d.
2.3.4. LC-ESI-TOF
LC-ESI-TOF echnique ( imsTOF, mass spec ome e , B uke , Mas-
sachuse s, USA) was used o con i m he iden i y o he oligome s
ex ac ed om he polyes e coa ings. The ch oma og aphic and mass
spec ome y condi ions we e he same as hose used in LC-MS/MS
analysis. MS da a we e acqui ed in a ull scan mode in a ange o
50–1000 m/z.
2.3.5. Sample ea men
2.3.5.1. Can coa ings. The can coa ings we e ex ac ed using ACN. Once
he cans we e emp y and clean, hey we e ex ac ed by illing wi h he
sol en and s o ed a 40ºC o 24 h. Nex , an aliquo o 5 mL was
emo ed and concen a ed o d yness wi h ni ogen, he esidue was
edissol ed wi h 0.2 mL o ACN and wi h 0.2 mL o 20%ACN o epoxy
and polyes e esins analysis, espec i ely. Then, he esul ing ex ac s
we e il e ed h ough a PTFE memb ane (0.22 µm po e size) be o e he
ch oma og aphic analysis.
2.3.5.2. Foods
2.3.5.2.1. Bisphenols and BADGEs. Bisphenols and BADGE de-
i a i es we e ex ac ed om he canned ood samples in acco dance
wi h he me hod p oposed by Les ido-Ca dama e al. (2021). The anal-
ysis was pe o med in duplica e. Samples con aining bo h solid and
liquid ac ions we e sepa a ed and ea ed independen ly. Fo he
me hod alida ion, una in oli e oil and he co e ing liquid o s u ed
squid we e used o eco e y es s. Fo i ied samples we e ex ac ed as
men ioned abo e.
*ne weigh , * *d ained weigh , PET polye hylene e eph hala e.
P. V´
azquez-Lou ei o e al.
Food Packaging and Shel Li e 40 (2023) 101183
4
2.3.5.2.2. Polyes e monome s and oligome s. Polyes e monome s
we e ex ac ed using QuEChERS. The ex ac ion was ca ied ou on he
basis o he p ocedu e epo ed by D i ield e al. (2018). B ie ly, o 10 g
o sample p e iously homogenized was added 10 mL o ACN and he
mix u e was shaken in a labo a o y shake . Then, he QuEChERS sal s
we e added and he mix u e was hand-shaken o 1 min. Nex , he ex-
ac s we e cen i uga ed (He ich Zen i ugen Uni e sal 320 R) a 2000
pm o 20 min and 5 mL o he supe na an was emo ed and placed in a
ial. The ex ac was concen a ed o d yness unde ni ogen gas a a
empe a u e o 35 ◦C. Finally, hey we e econs i u ed wi h 0.5 mL o
ACN and 0.5 mL o 0.1% o mic acid in wa e , con aining he in e nal
s anda d (PAd4) a a inal concen a ion o 5 mg/L, and il e ed h ough
a 0.22 µm PTFE il e . Reco e y assays o polyes e monome s we e
pe o med in spiked len ils samples.
To ex ac he polyes e oligome s, 5 g o sample was weigh in a ube
o Te lon and 10 mL o ACN we e added. The ube was capped and
placed in an ul asonic ba h (B anson 5510 (Danbu y, CT, USA)) o 2 h
and hen cen i uged a 2500 pm o 5 min. Fi e mL o he supe na an
was placed in a clean ial and concen a ed o d yness unde gen le
ni ogen low a 40 ◦C and econs i u ed wi h 0.5 mL o 20%ACN:H
2
O
( / ). The esul ing ex ac was il e ed h ough a 0.22 µm PTFE il e
and ans e ed in o a ial o be analysed.
2.3.6. Exposu e assessmen
The exposu e was es ima ed by combining he mig a ion da a,
namely he concen a ion o mig an s eleased om he can coa ing in
ood, wi h consump ion da a ob ained om he Spanish Na ional Su ey
o adul popula ion ENALIA-2.
I should be no ed ha o analy ical esul s lowe han he limi o
quan i ica ion (LOQ) and limi o de ec ion (LOD) alues equal o LOQ/
2 and LOD/2 espec i ely we e conside ed acco ding o he GEMS/
Food–EURO ecommenda ions (GEMS-Food Eu o, 1995; Si o , Homme ,
Ta d & Leblanc, 2012).
3. Resul s and discussion
3.1. Iden i ica ion o polyme ic ood con ac coa ings
The inne coa ings o me al cans we e en a i ely iden i ied by FTIR.
As can be in e ed om Table 1 di e en coa ings a e cu en ly being
used. Se e al o he samples analysed inco po a ed coa ings en a i ely
iden i ied as epoxy-based esins. This ype o coa ing is s ill used, i
p esen s good mechanical p ope ies, chemical esis ance and in addi-
ion i is compa ible wi h mo e ood ypes han o he coa ings. Howe e ,
owing o he conce ns abou he po en ial e ec s o bisphenol A on
consume s’ heal h, i s use is being eplaced by o he al e na i e
coa ings.
Polyes e -based esins a e one o he newe coa ings ha a e being
used, ne e heless, hey a e no app op ia e o e y agg essi e and
acidic oods. Fi e o he samples analysed in his s udy had polyes e -
based coa ings in he body o he can. The pH o he oods packed in
hese cans a ied be ween 5.2 and 6.4. In 9 o he 11 samples con aining
oods wi h a pH alue below 5.5, an epoxy coa ing was iden i ied.
O he samples, speci ically AC, BN, CH, CTO, CAG, CAO, SCO, TOT,
TOR, JU and ME we e en a i ely iden i ied as an ac ylic base, ob aining
good ma ches wi h he FTIR spec al lib a ies, bu he analysis o he
chemical mig a ion p o ile a e ex ac ion e ealed ha he coa ing was
clea ly based on a BADGE esin. Since epoxy esins adhe e well o he
me al su aces hey a e usually used as a base coa o ac ylic coa ings
(LaKind, 2013), his ac could explain hese esul s. In addi ion, i is also
in e es ing o highligh ha FTIR-ATR me hods a e used o analyse he
sample su ace wi hin 1–2 µm in dep h, which would suppo he
iden i ica ion o he supe icial laye as ac ylic base.
3.2. Food sample ex ac ion p ocedu e
3.2.1. Canned ood
Fo bisphenols and BADGE de i a i es, a sol en ex ac ion-based
me hod was ca ied ou because o i s simplici y and e sa ili y o be
applied o a wide a ie y o canned oods. The me hod consis ed o h ee
main s eps homogeniza ion, sol en ex ac ion, and cen i uga ion as a
clean-up p ocess o emo e solid pa icles. The mix u e o n-hep ane, o
a emo al, and ACN90% p o ed o be an app op ia e ex ac ion sol-
en o epoxy mig an s achie ing eco e ies >63% (Goodson, Robin,
Summe ield & Coope , 2004, Les ido-Ca dama e al. 2021).
Th ee di e en me hods we e assayed o ex ac ca boxylic acids
om he canned oods, speci ically i) sol en ex ac ion, ii) solid-phase
ex ac ion and iii) a QuEChERS me hod. The me hods we e e alua ed
based on he eco e ies o he analy es. Thus, ACN was used as sol en
since i has shown o be e icien in he ex ac ion o mig an s (Pasei -
o-Ce a o, DeJage & Begley, 2019; D i ield e al. 2018). A concen a-
ion s ep was necessa y due o he low concen a ion o he monome s in
ood. Unde hese condi ions ai ly low eco e ies (<40%) we e ob-
ained. Fu he , solid-phase ex ac ion using an SPE ca idge (Agilen
Bond Elu C18, 500) and ACN con aining 0.1% o mic acid as ex ac ion
sol en was also ied, bu lowe eco e ies (<30%) we e achie ed.
The QuEChERS app oach (D i ield e al. 2018) p o ided he bes
esul s in e ms o eco e ies (>92%) and, in addi ion, i is conside ed a
con enien al e na i e o adi ional me hods based on he p inciples o
he g een chemis y (San ana-Mayo , Socas-Rod íguez, He e a-He e a
& Rod íguez-Delgado, 2019), he e o e i was selec ed o pe o m he
analyses.
Oligome s we e ex ac ed by a common sol en ex ac ion me hod
wi h ACN ollowed by cen i uga ion and concen a ion s eps. Due o he
low amoun s o a ailable analy ical s anda ds, he e ec i eness o he
clean-up p ocedu e could no be e alua ed. Howe e , wi h his
app oach he ma ix e ec s ep esen a signi ican limi a ion.
3.3. Ch oma og aphy, de ec ion, and iden i ica ion
Based on p e ious wo ks and he da a epo ed in he li e a u e a
gene ic g adien consis ing o ACN and wa e was op imized o he
analysis o epoxy mig an s. Di e en elu ion p og ams and low a es
we e ied. Mo eo e , ou columns speci ically, Kine ex C18 100 A
(150 ×2.1 mm, 2.6 µm); Kine ex C18 100 A (150 ×2.1 mm, 5 µm);
K omaphase C18 100 (150 ×3 mm, 5 µm) and Phenosphe e (ODS)2 80 A
(150 ×4.6 mm, 3 µm) we e es ed. When using he Kine ex columns he
sepa a ion o mos compounds esul ed in spli peaks and a poo ch o-
ma og aphic esolu ion o BPA and BADGE⋅H
2
O.HCl was obse ed wi h
he K omaphase C18 column.
The Phenosphe e (ODS)2 s a iona y phase and he g adien s a ed
wi h 20% o ACN and inc eased o 100% in 40 min p o ided an
app op ia e sepa a ion o he analy es. Unde he same ch oma o-
g aphic condi ions LC-MS/MS was used as a con i ma o y echnique.
Since se e al coa ings we e en a i ely iden i ied as ac ylic esins,
he ch oma og aphic me hod (HPLC-DAD) was applied o hese samples
o y o iden i y ac ylic de i a i es. Based on a s udy epo ed in he
li e a u e se e al wa eleng hs we e selec ed (Pasei o-Ce a o, DeV ies,
& Begley, 2017). Th ee peaks wi h di e en UV spec a om phenolic
compounds, namely a
R
=6.2 (λ max. 226, 264, 362),
R
=16.6 (λ max.
290) and
R
=23.2 (λ max. 226, 268) we e de ec ed in bo h coa ings and
oods (BN, CTO, CAG, CAO, SCO and AC). The samples we e also ana-
lysed by he LC-MS/MS me hod, bu he iden i y o hese 3 compounds
could no be es ablished., as no s uc u al in o ma ion was gained om
he mass spec a ob ained. A s anda d o bisphenol A e hoxyla e dime-
ac yla e was injec ed unde he same condi ions bu he e en ion ime
did no ma ch he e en ion ime o he unknown compounds, he e o e
hey emained as uniden i ied mig an s.
The sepa a ion o ca boxylic acids was achie ed using a Gemini
(C18, 110 A, 150×3mm, 5 µm) column. Two di e en acids, speci ically
P. V´
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Food Packaging and Shel Li e 40 (2023) 101183
5
0.1%( / ) TFA and 0.1% o mic acid, we e es ed o acidi y he mobile
phase. Bo h acids e ealed a sui able sepa a ion o he monome s.
Howe e , al hough 0.1%TFA p o ided he bes esolu ion, due o i s
dange ousness, 0.1% o mic acid was chosen o subsequen analysis.
Full-scan analyses we e pe o med o e he ange o 100–1000 m/z
in posi i e mode o he de ec ion o polyes e oligome s and se e al
peaks we e de ec ed. Masses we e compa ed o an in-house oligome
da abase buil wi h he common monome s used in he polyes e coa ing
o mula ions. The adduc s o Na
+
, K
+
, NH
4
+
, H
+
we e conside ed. Only
oligome s wi h a molecula weigh up o 1000 m/z we e conside ed
since i is assumed ha highe molecula weigh compounds a e non-
abso bable in he gas oin es inal ac .
Th ee o he oligome s en a i ely iden i ied in he polyes e coa ings
we e also ound in se e al ood samples, speci ically 2 TPA+BD/
MBO+DEG(C) o 2 TPA+EG+HMP(C), TPA+PG+EG(L) and 2 TPA+EG
(L). In he case o 2TPA+BD/MBO+DEG (o 2TPA+HMP+EG)(C) he
p o ona ed molecula ion and he sodium adduc we e obse ed a m/z
437.2 and m/z 459.2, espec i ely. The sodium adduc was chosen o
quan i a i e analysis. Fo 2TPA+EG, he p o ona ed molecule (m/z
359.1) and he ammonium adduc (m/z 376.1) we e de ec ed, his las
one was used o quan i ica ion pu poses. Whe eas o TPA+PG+EG(L)
only he sodium adduc (m/z 291.1) was de ec ed. The selec ed adduc s
we e hose ha p o ided he highes in ensi y. These esul s we e also
ob ained by exac mass analysis using a LC-TOF-MS unde he same
ch oma og aphic condi ions. Thus, hese h ee oligome s we e de ec ed
a con idence le el 4 acco ding o he Schymanski scale (Schymanski
e al. 2014).
As ega ds o he oligoes e s syn hesised, (2NPG+2iPA(L), 2NPG+
2iPA(C), 4NPG+4iPA(C)) he p o ona ed molecula ions (m/z 487.2; m/
z 469.2) as well as he sodium, (m/z 509.2; m/z 491.2; m/z 959.3)
ammonium (m/z 504.2; m/z 486.2; m/z 954.3) and po assium (m/z
525.2; m/z 507.1; m/z 975.3) adduc s, espec i ely we e obse ed. In
he case o 4NPG+4IPA(C) he p o ona ed molecule was no de ec ed,
which is in line wi h Ca iou e al. (2022). 2NPG+2iPA(C) was iden i ied
and subsequen ly quan i ied in se e al ood samples, p ecisely LEV,
SCA_L, PAT_A and PAT_L, a concen a ions be ween 0.27 and 0.91
μ
g/g.
3.4. In-house me hod alida ion
Bo h me hods, HPLC-FLD o bisphenols and BADGE de i a i es and
LC-MS/MS o ca boxylic acids we e alida ed ega ding linea i y,
sensi i i y, epea abili y, in e media e p ecision and eco e y.
The quan i ica ion was pe o med by cons uc ing calib a ion cu es
using six concen a ion le els o bisphenols, BADGE de i a i es and
ca boxylic acids and ou concen a ions le els o BHET and 2NPG+
2iPA(C), and hey we e adjus ed o a linea equa ion. Each calib a ion-
poin is he a e age o wo measu emen s. The linea equa ions o he
calib a ion cu es, and o he linea i y pa ame e s a e shown in Table 2.
All compounds exhibi ed app op ia e linea i y o e he ange s udied
wi h
2
alues ≥0.9230.
The limi s o de ec ion (LOD) and quan i ica ion (LOQ) we e es i-
ma ed acco ding o ACS guidelines (3:1 and 10:1 signal- o noise,
Table 2
Me hod alida ion (linea i y, epea abili y, eco e ies and in e media e p ecision).
Tuna (BN_A) S u ed squid’s oil
Reco e y (%) In e media e
p ecision (R.S.D.
%) (n =6)
Reco e y (%) In e media e
p ecision (R.S.D.
%) (n =6)
Compound Range o
linea i y (mg/kg)
Equa ion R
2
Repea abili y
(RSD%)
0.05 0.1 0.2 0.05 0.1 0.2 0.05 0.1 0.2 0.05 0.1 0.2
BADGE .2 H
2
O 0.04–1 y =1076.3x -
4.2117
0.9998 9 - - - - - - 82 90 71 20 16 11
BPF 0.04–1.0 y =508.26x +
0.6257
0.9999 13 - - - - - - 75 76 70 9 11 7
BPE 0.04–1.0 y =477.61x +
2.1945
0.9997 12 77 78 83 17 15 18 79 77 79 18 13 15
BPA 0.04–1.0 y =621.58x +
0.833
0.9999 9 85 90 78 16 26 16 85 83 83 17 14 10
BADGE⋅H
2
O.
HCl
0.04–1.0 y =1135.7x -
5.4496
0.9999 9 81 86 72 11 17 14 78 70 63 13 13 5
BADGE⋅H
2
O 0.04–1.0 y =1227.8x -
5.2233
0.9998 8 95 80 70 21 10 9 83 72 64 25 5 8
BPB 0.04–1.0 y =819.51x -
1.4707
0.9998 10 95 87 72 22 24 5 80 76 67 19 6 13
BADGE.2HCl 0.04–1.0 y =1165.7x +
1.123
0.9999 6 102 82 81 19 11 6 90 79 72 18 11 9
BADGE.HCl 0.04–1.0 y =999.06x -
4.687
0.9999 9 90 69 75 10 13 7 71 71 71 16 12 9
BADGE 0.04–1.0 y =1399.4x -
6.3097
0.9999 6 78 86 70 12 27 3 77 73 71 12 11 4
BPG 0.04–1.0 y =935.23x -
3.6629
0.9997 10 78 71 74 10 5 5 78 71 75 20 4 14
CyclodiBADGE 0.04–2.0 y =1152.3x +
5.3623
0.9997 7 101 72 76 25 4 9 - - - - - -
Len ils (LEV)
Reco e y (%) In e media e P ecision (R.S.D.%) (n =6)
0.05 0.5 1.25 0.05 0.5 1.25
TPA 0.01–1.0 y =0.5385x +
0.0544
0.9958 2 137 107 99 15 22 16
PA 0.01–1.1 y =0.335x +
0.0125
0.9988 3 111 105 92 22 6 13
IPA 0.01–1.2 y =0.4429x +
0.0289
0.9978 5 129 106 97 12 18 12
BHET 1–20 y =27920x +
9449.8
0.9986
2NPG-2IPA (C) 0.1–1 y =3.8872x –
0.4601
0.9230
P. V´
azquez-Lou ei o e al.
Food Packaging and Shel Li e 40 (2023) 101183
6
espec i ely) (ACS, 1980). The LODs we e 0.010 mg/kg o bisphenols
and BADGE de i a i es excep o BPF and BPE o which a LOD o
0.020 mg/kg was achie ed. LOQs o 0.025 mg/kg o bisphenols and
BADGE de i a i es and 0.040 mg/kg o BPE and BPF, espec i ely we e
ob ained. The desc ibed me hods ha e su icien sensi i i y o de ec he
compounds a a concen a ion below he speci ic mig a ion limi (SML)
namely, 0.05 mg/kg o BPA (Commission Regula ion (EU) No 10/2011)
(Eu opean Union, 2011) and 9 mg/kg o he sum o BADGE and hei
hyd olysed de i a i es and 1 mg/kg o he sum o hei hyd ochlo ic
de i a i es (Regula ion (EC) No. 1895/2005)(Eu opean Union, 2005).
LODs and LOQs o 0.004 and 0.01 mg/kg, espec i ely, we e eached o
he ca boxylic acids, which was lowe han hose epo ed by B enz,
Linke, & Sima , 2017 using HPLC-DAD.
In addi ion, he LOD; LOQ o BHET and 2NPG+2iPA(C) we e
de e mined ob aining alues o 0.1; 0.2 and 0.05; 0.1 mg/kg,
espec i ely.
Repea abili ies de e mined analysing se en eplica es o he s an-
da ds a one concen a ion le el, 0.1 mg/kg o bisphenols and BADGE
de i a i es and 0.02 mg/kg o ca boxylic acids and exp essed as RSD
(RSD% (n =7)) we e ≤13% and ≤5% espec i ely.
In e media e p ecision and eco e ies we e e alua ed by he addi-
ion o known amoun s o he a ge compounds o ood a h ee con-
cen a ions le els, speci ically 0.05, 0.1 and 0.2 mg/kg o bisphenols
and BADGE de i a i es and 0.05, 0.5 and 1.25 mg/kg o PA, TPA and
IPA, and in h ee sepa a e days by duplica e (n =6 eplica es). Since
hese compounds usually mig a e in a g ea e ex en o a y oods
(Cabado e al. 2008; Les ido-Ca dama e al. 2021), una and he co e ing
liquid o squid (sun lowe oil) we e selec ed as ep esen a i e o oily
solid ood and co e ing liquid o conduc he eco e y assays.
Fo bisphenols and BADGE de i a i es, eco e ies anged om 63%
o 102%. The eco e ies o BADGE .2 H
2
O and BFE in una and cyclo-
diBADGE in s u ed squid’s oil a e no epo ed due o ma ix in-
e e ences hampe ing good es ima ion. This beha iou has also been
p e iously epo ed o BADGE in a samples (Rau e , Dickinge , Zih-
la z & Lin schinge , 1999).
Ca boxylic acid eco e ies a ied be ween 92% and 137%. The wo s
eco e y alue (137%) was ob ained o TPA a a concen a ion o 0.05
mg/kg. In connec ion wi h hese esul s, Pasei o-Ce a o, DeJage , &
Begley (2019), in es iga ed he mig a ion o hese monome s in canned
oods and ob ained poo eco e ies o TA in mos o he samples ana-
lysed. The poo eco e y measu ed o TPA a a spiked concen a ion o
0.05 mg/kg sugges s ha he ex ac ion p ocedu es should be op imized
and imp o ed o analyse he monome in he di e en ood i ems. In he
p esen s udy a gene ic p ocedu e was applied o de e mine he mono-
me s in oods as a p ac ical and comp omise analy ical solu ion o he
di e en ood ma ices. Howe e , despi e his poo eco e y alue ac-
co ding o Eu opean Commission (EC) guidelines (Eu opean Commis-
sion Di ec o a e Gene al o Heal h and Food Sa e y, 2017), conside ing
he me hod pe o mance accep abili y c i e ia, accep able mean eco -
e y alue wi hin he 70–120% ange we e ob ained o he o he
monome s.
The p ecision alues exp essed as RSD% anged be ween 3% and
27%. All alues we e <25% excep o BPA (26%) and BADGE (27%) in
a una sample spiked a a concen a ion o 0.1 mg/kg. Fo BPA, he e-
sul s we e compa able o hose epo ed by Tza za akis e al. (2017)
om 7.9% o 17.5% in so d inks, liquid and solid phase o canned ood.
RSD% alues ob ained o ca boxylic acids we e ≤22%.
3.5. Concen a ion o mig an s in canned oods u s
3.5.1. Bisphenols and BADGE de i a i es
The HPLC-FLD me hod was used o analyse bisphenols and BADGEs
in canned oods. The concen a ions ob ained a e p esen ed in Table 3.
Th ee BADGE de i a i es (BADGE .2 H
2
O, BADGE⋅H
2
O.HCl and cyclo-
diBADGE) and BPA we e de ec ed abo e he LOD in mo e han 50% o
he samples. Gene ally, he oods wi h he highes concen a ions o
BADGE de i a i es, pa icula ly cyclodiBADGE, and BPA we e hose
wi h he highes a con en (e.g., BN_A (16% a ); CAO_A (12% a )).
Con e sely, lowe concen a ions we e ound in low- a oods (e.g.,
TOE_A (0.1% a ); CHA_L (0.1% a )). These esul s a e in ag eemen
wi h hose epo ed by Cabado e al. (2008) who ound ha he
mig a ion o BADGE and BFDGE occu s o a la ge ex en in high- a
oods. Conside ing ood ca ego ies sea ood p oduc s p esen ed he
highes concen a ions o he a ge analy es and ege ables he lowes .
This end was also obse ed in a p e ious wo k (Les ido-Ca dama e al.
2021). O all moni o ed mig an s, he highes concen a ion ound was
4.01
μ
g/g o cyclodiBADGE in a sample o macke el ille s in sun lowe
oil. This esul is compa able o ha ob ained in a p e ious wo k in
which a concen a ion o 3.59
μ
g/g was ound in a sample o mussels
(Les ido-Ca dama e al. 2021). I is wo h men ioning ha in many
samples highe concen a ions we e de ec ed in he co e ing liquids
han in he solid oods. Biede mann, Zu luh, G ob, Vedani, and
B üschweile (2013) epo ed lowe alues o cyclodiBADGE, speci -
ically o e he ange o <0.025–1.98
μ
g/g in canned ish. The accep -
able mig a ion le el o 0.05
μ
g/g s a ed by he B R in i s opinion (B R
Opinion 022/2016) was exceeded in mos o he samples analysed in his
s udy.
Rega ding BADGE .2 H
2
O and BADGE⋅H
2
O.HCl, he ound concen-
a ions anged om <LOD o 0.65
μ
g/g and om <LOD o 0.09
μ
g/g,
espec i ely. All samples we e below he es ic ion le els (Regula ion
Table 3
Concen a ions o bisphenol A and BADGE de i a i es in canned oods u s.
Compound concen a ion (µg/g)
Sample BADGE .2 H
2
O BPA BADGE⋅H
2
O.HCl CyclodiBADGE
BN_A 0.65 0.05 0.04 0.41
BN_L 0.16 0.02 <LOD 0.49
CH_A 0.11 0.04 <LOD 0.30
CH_L <LOD <LOD <LOD 2.78
CTO_A 0.51 0.06 0.07 0.55
CTO_L 0.11 <LOD <LOD 1.22
CAG_A 0.43 0.08 0.09 0.71
CAG_L 0.03 0.04 <LOD 4.01
CAO_A 0.51 0.09 0.11 0.49
CAO_L 0.31 0.03 <LOD 3.63
SCO_A 0.52 0.04 0.06 0.44
SCO_L 0.26 <LOD <LOD 2.44
ME_A 0.09 <LOD <LOD 0.11
ME_L <LOD <LOD <LOD 0.72
AC_A 0.64 0.07 0.06 1.19
AC_L 0.09 <LOD <LOD 0.99
AL_A 0.11 <LOD <LOD 0.07
RAV_A 0.11 <LOD <LOD <LOD
RAV_L 0.07 <LOD <LOD 0.69
PM_A 0.09 0.08 <LOD 0.03
PM_L 0.06 <LOD <LOQ <LOD
GUIM_A 0.37 0.13 0.05 0.09
GUIM_L 0.06 <LOD <LOD <LOD
TOE_A 0.08 <LOD <LOQ 0.02
TOE_L 0.07 <LOD <LOD 0.02
CHA_A 0.31 0.09 0.07 0.05
CHA_L 0.06 <LOD <LOD <LOD
TOT <LOD <LOD <LOD <LOD
TOR_A 0.05 <LOD <LOD 0.03
TOR_L 0.05 <LOD <LOD <LOD
JU_A 0.13 0.04 0.05 0.07
JU_L <LOD <LOD <LOD <LOD
GUIB_A <LOD <LOD <LOD <LOD
GUIB_L <LOD <LOD <LOD <LOD
LOD BADGE.2H2O; BPA; BADGE. H2O.HCl; CyclodBADGE: 0.010 mg/kg.
LOQ BADGE .2 H
2
O; BPA; BADGE⋅H
2
O.HCl; CyclodBADGE: 0.025 mg/kg.
(Median: BADGE .2 H
2
O: 0.11; BPA:0.055; BADGE⋅H
2
O.HCl:0.06; Cyclo-
diBADGE:0.49).
(Max. alue: BADGE .2 H
2
O: 0.65; BPA:0.13; BADGE⋅H
2
O.HCl:0.11; Cyclo-
diBADGE:4.01).
_A e e s o solid ac ion.
_L e e s o liquid ac ion.
P. V´
azquez-Lou ei o e al.
Food Packaging and Shel Li e 40 (2023) 101183
7
(EC)No 1895/2005)(Eu opean Union, 2005). In compa ison, ou esul s
a e analogous o hose epo ed by Míguez, He e o, Quin ´
as, Rod íguez,
Gigosos, and Ma iz (2012) in ish p oduc s and lowe han hose ound
by Alabi, Caballe o-Case o, & Rubio, (2014) in canned ege able p od-
uc s, ish and o he sea ood.
Fo BPA he concen a ions ob ained we e in he ange o
<LOD–0.09
μ
g/g. These esul s we e simila o hose ound by Mun-
guía-L´
opez, M., Ge a do-Lugo, Pe al a, Bolumen, & So o-Valdez (2005)
in una ish and lowe han hose epo ed by Sajiki, Miyamo o, Fuka a,
Mo i, Yonekubo, and Hayakawa (2007) in canned ood sold in Japanese
ma ke s. Se en o he analysed samples (CTO_A, CAG_A, CAO_A, AC_A,
PM_A, GUIM_A, CHA_A) exceeded he SML o 0.05 mg/kg (Regula ion
[EU] No. 2018/213)(Eu opean Union, 2018), and in h ee o hem BPA
mig a ed in a quan i y mo e han wice he SML. Following he new TDI
es ablished in he EFSA d a e-e alua ion o BPA, i is p obably ex-
pec ed ha he cu en SML could be e ised, and i could be lowe ed.
Conside ing he esul s ob ained in his s udy i he speci ic mig a ion
limi is lowe ed, he samples wi h BPA concen a ions close o he
cu en SML (e.g., CH_A, CAG_L, SCO_A, JU_A) would be he ones mos
likely o be a ec ed.
Las ly, i is wo h men ioning ha di e ences in he concen a ion o
BADGE .2 H
2
O and cyclodiBADGE we e obse ed depending on he
composi ion o he co e ing liquid in he macke el ille s samples (CTO,
CAG, CAO). Thus, he highes concen a ions we e ound in he oily
media, oli e oil in he case o BADGE .2 H
2
O and sun lowe and oli e oil
o cyclodiBADGE, and on con a y he lowes concen a ions we e
ound in he co e ing sauce o oma o. This obse a ion is in acco dance
wi h ha epo ed by Cabado e al. (2008), who s udied he in luence o
he co e ing sauce on he mig a ion BADGE and BFDGE and ound
highes concen a ions in he oods wi h he highes le els o a .
3.5.2. Monome s and polyes e oligome s
An o e iew o he concen a ions o he monome s de ec ed in he
samples analysed is p esen ed in Table 4. The concen a ions o he in-
di idual monome s anged om <LOD o 0.047
μ
g/g o TPA, om
<LOD o 0.022
μ
g/g o PA and om <LOD o 0.013
μ
g/g o IPA. TPA
was de ec ed in almos all samples analysed, in con as , IPA was
de ec ed in only six samples (GUIB, AL, GUIM_L, RAV_L, PAT, PAT_L).
The TPA concen a ions a e consis en wi h hose epo ed by Pasei -
o-Ce a o e al. (2019), howe e , he concen a ions o IPA ound in his
s udy a e lowe han hose desc ibed by he men ioned au ho s.
The de ec ed concen a ions o he monome s we e in all samples
much lowe han he speci ic mig a ion limi s (SML) (IPA 5 mg/kg; TPA
7,5 mg/kg) (Commission Regula ion (EU) No 10/2011)(Eu opean
Union, 2011). Among he samples analysed i was no possible o
es ablish a clea endency be ween he concen a ion o he monome s
and he ood composi ion (i.e., a con en ).
Fou oligome s p e iously iden i ied in he polyme ic coa ings (i.e., 2
TPA+BD/MBO+DEG(C) o 2 TPA+EG+HMP(C); TPA+PG+EG(L);
2TPA+EG(L) and 2NPG+2iPA(C) we e de ec ed in se e al ood sam-
ples. Due o he lack o analy ical s anda ds no con i ma ion o iden i y
was pe o med o he i s h ee oligome s. BHET was used as a p oxy
o he semi-quan i ica ion o oligome s. None heless, o 2NPG+2iPA
(C) he con i ma ion o he iden i y was ca ied ou by using he syn-
hesised s anda d. The es ima ed concen a ions o he oligome s a e
gi en in Table 4. 2 TPA+BD/MBO+DEG(C) was de ec ed a concen-
a ions anging om <LOD o 1.37
μ
g/g, being a sample o g een peas
he one ha p esen ed he highes concen a ion. 2NPG+2iPA(C) was
de ec ed in se e al samples a concen a ions a ying be ween <LOD
and 0.91
μ
g/g, whils TPA+PG+EG and 2TPA+EG we e only de ec ed in
one sample; he quan i ica ion o his las oligome was no possible due
o he ma ix e ec leading o signal enhancemen . Compa ing ou
Table 4
Concen a ion o polyes e monome s and es ima ed concen a ion o oligome s in canned oods u s.
Compound concen a ion (µg/g)
Sample TPA PA IPA 2TPA+EG (L) (NH
4
+
) 2TPA+BD/MBO+DEG (C)/2TPA+EG+HMP (C) (Na+) TPA+PG+EG (L) (Na+) 2NPG+2IPA (C) (NH
4
+
)
LEV 0.018 <LOQ <LOD <LOD 1.12 <LOD 0.37
LE 0.047 <LOD <LOD <LOD 0.48 0.24 <LOD
GUIB_A 0.025 <LOQ <LOQ * 1.37 <LOD <LOD
GUIB_L 0.03 <LOQ <LOD <LOD <LOD <LOD <LOD
SCA_A <LOD <LOD <LOD <LOD <LOD <LOD <LOD
SCA_L <LOD <LOD <LOD <LOD <LOD <LOD 0.45
AL <LOQ <LOD <LOQ <LOD <LOD <LOD <LOD
PM_A <LOD <LOD <LOD <LOD <LOD <LOD <LOD
PM_L <LOQ <LOD <LOD <LOD <LOD <LOD <LOD
GUIM_A <LOQ <LOQ <LOD <LOD <LOD <LOD <LOD
GUIM_L <LOQ <LOQ <LOQ <LOD <LOD <LOD <LOD
CHA_A <LOQ <LOD <LOD <LOD <LOD <LOD <LOD
CHA_L <LOQ <LOD <LOD <LOD <LOD <LOD <LOD
TOT <LOD 0.022 <LOD <LOD <LOD <LOD <LOD
TOR_A <LOD <LOD <LOD <LOD <LOD <LOD <LOD
TOR_L <LOD 0.006 <LOD <LOD <LOD <LOD <LOD
RAV_A <LOQ <LOQ <LOD <LOD <LOD <LOD <LOD
RAV_L 0.01 0.009 <LOQ <LOD <LOD <LOD <LOD
TOE_A <LOD <LOQ <LOD <LOD <LOD <LOD <LOD
TOE_L <LOQ 0.009 <LOD <LOD <LOD <LOD <LOD
PAT_A 0.016 <LOD 0.013 <LOD <LOD <LOD 0.91
PAT_L 0.02 <LOD 0.013 <LOD <LOD <LOD 0.27
JU_A <LOD <LOD <LOD <LOD <LOD <LOD <LOD
JU_L <LOD <LOD <LOD <LOD <LOD <LOD <LOD
BD: bu anediol (1,3 and 1,4); DEG: die hylene glycol; EG: e hylene glicol; HMP: 1,1,1-T is(hyd oxyme hyl)p opane; MBO:2-me hyl-1,3-p opanediol; PG: p opylene
glycol (1,2 and 1,3).
(L):linea ; (C): cyclic
LOD TPA, PA, IPA: 0.004 mg/kg; LOD BHET: 0.1 mg/kg LOD 2NPG+2IPA (C): 0.05 mg/kg.
LOQ TPA, PA, IPA: 0.01 mg/kg; LOQ BHET: 0.2 mg/kg LOQ 2NPG+2IPA (C): 0.1 mg/kg.
(*) No quan i ied.
(Median: TPA:0.02; PA:0.009; IPA:0.013; 2TPA+BD (C):1.12; TPA+PG+EG(L): 0.24; 2NPG+2IPA(C): 0.41).
(Max. alue: TPA:0.047; PA:0.022; IPA:0.013; 2TPA+BD (C):1.37; TPA+PG+EG(L): 0.24; 2NPG+2IPA(C): 0.91).
_A e e s o solid ac ion; _L e e s o liquid ac ion.
P. V´
azquez-Lou ei o e al.
Food Packaging and Shel Li e 40 (2023) 101183
8
esul s wi h o he s udies ecen ly published on he occu ence o
polyes e oligome s in canned oods u s (Pasei o-Ce a o e al. 2019;
Ca iou e al. 2022), he es ima ed concen a ions ob ained in his wo k
we e sligh ly highe . These di e ences could be due o he di e en
ypes o coa ings, e en also o he di e en ypes o canned oods.
3.6. Die a y exposu e assessmen
The die a y exposu e da a (mean and 95 h pe cen ile) o chemicals
(i.e., bisphenols, BADGE de i a i es and polyes e monome s and olig-
ome s) ans e ed om ood con ac coa ings o me al cans a e sum-
ma ized in Tables 5 and 6. To es ima e he exposu e, bo h he liquid and
solid ac ions we e conside ed as a whole sample.
Rega ding epoxy mig an s, es ima ed mean die a y exposu e anged
om 0.000646 o 0.670
μ
g/kg bw/day o BADGE .2 H
2
O and be ween
0.000646 and 0.235; 0.000646–0.104 and 0.000646–0.671
μ
g/kg bw/
day o BPA, BADGE⋅H
2
O.HCl and cyclodiBADGE, espec i ely.
CTO, CAO, CAG and AC we e iden i ied o be he majo con ibu o s
o he adul BPA and BADGE de i a i es exposu e wi hin he sea ood
p oduc s ca ego y and GUIM and JU wi hin he ege able ca ego y.
In gene al, he exposu e le els o BADGE de i a i es ob ained in his
s udy we e low, in all cases below he TDI o 0.15 mg/kg bw/day o
BADGE and i s hyd olysis p oduc s (EFSA, 2004, EFSA, 2015). In he
case o BPA, he calcula ed die a y in akes we e in all cases below he
empo a y ole able daily in ake ( -TDI) o 4
μ
g/kg bw/day, bu how-
e e we e highe han he ecen TDI p oposed in he EFSA d a
opinion. Thus, by compa ing he new TDI wi h he die a y exposu e
es ima ion o BPA, he consume s wi h bo h a e age and high exposu e
o BPA in he popula ion g oup s udied exceeded he new TDI. These
esul s con i m he exposu e da a epo ed in he li e a u e (Zhou e al.
2019; Liao and Kannan, 2013). The lowe TDI ecommended by EFSA
can also a ec he indus ial p ac ices, in he sense ha hey should
ca y ou a s ic e con ol o he ma e ials hey use o ensu e ha hey
comply wi h he limi s.
Conce ning he polyes e monome s, e y limi ed in o ma ion on
exposu e o hese chemicals has been epo ed in he li e a u e; he
esul s ob ained in his s udy a ied be ween 0.000517 and 0.0851
μ
g/
kg bw/day. LEV and GUIB u ned ou o be he main con ibu o s. Ou
da a we e sligh ly lowe han he die a y exposu e le els (0.01–0.13
μ
g/
kg bw/day) o TPA mig a ed om PET epo ed by Shin, Kim, Kim, Kim,
Song & Oh, 2021, and well below he e e ence dose (R D) o 1.0 mg/kg
bw/day (Shin e al. 2021).
The die a y exposu e o oligome s has been sca cely s udied,
ecen ly. Tsocha zis e al. (2020) in es iga ed he exposu e o PET
oligome s mig a ed om eabags. The au ho s concluded ha he
h eshold o 90
μ
g/day/pe son was no exceeded wi h a single con-
sump ion. As ega ds ou s udy, he es ima ed exposu e a ied be ween
0.00646 and 2.75
μ
g/kg bw/day. Len ils (LEV) and he g een peas
(GUIB) appea ed o be majo con ibu o s o die a y exposu e. The
highes alues co esponded o he cyclic oligome s, which is pa icu-
la ly in e es ing o se e al easons. On he one hand, hese molecules
belong o C ame class III (high oxici y), especially hose o med om
a oma ic dica boxylic acids TPA o IPA (Ecka d , He zel, B enz & Sima ,
2020) and, on he o he hand, usually he oligome s oge he wi h im-
pu i ies and eac ion p oduc s a e he g ea es mig a ing subs ances
(G ob, 2014). Rega ding he h eshold o oxicological conce n (TTC)
app oach i is in e es ing o no e ha C ame ules a e used as a
sc eening ool o es ima e he oxici y o a gi en compound when oxi-
cological da a do no exis o a e e y limi ed. The exposu e assessmen
used should o e es ima e die a y exposu e o high consume s using
conse a i e assump ions in pa icula in wha conce ns o ood con-
sump ion and chemical concen a ions (EFSA and WHO, 2016). Mole-
cules belonging o C ame class III include s uc u al ea u es ha
pe mi no s ong ini ial imp ession o sa e y o may e en sugges sig-
ni ican oxici y, he h eshold o oxicological conce n (TTC) es ab-
lished o hese molecules is 90 µg/pe son/day. S uc u es indica i e o
po en ial high oxici y include alipha ic seconda y amino, cyano,
halogeno-compounds, e c. many o hem a e Class III because hey un-
de go me abolic bioac i a ion o po en ially oxic chemical en i ies.
Addi ionally, neu o oxins, e a ogens o endoc ine dis up ing chemicals
should be conside ed as sepa a e classes (Pa lewicz, Wambaugh, Fel e ,
Simon & Becke , 2018; K oes e al. 2004). Al hough high exposu e o
class III molecules could ep esen heal h conce ns, howe e , hese e-
sul s need o be conside ed ca e ully, since any exposu e assessmen is
con on ed wi h a numbe o unce ain ies ela ed o he concen a ion
o chemicals in ood and he ood consump ion su eys (K oes e al.
2002).
4. Conclusions
Ta ge ed and non- a ge ed me hodologies we e applied o de e mine
mig an s ans e ed om polyme ic coa ings, speci ically epoxy and
polyes e , in o canned oods u s.
Sample ex ac ion p ocedu es we e op imized o he di e en ana-
ly es. O e all sa is ac o y esul s we e ob ained. Howe e , in some
ma ices (e.g., s u ed squid’s oil) and o ce ain analy es, he me hod
should be imp o ed o achie e op imal pe o mances. As ega ds he
concen a ion o he mig an s in oods and despi e he limi ed numbe o
samples es ed, i is in e es ing o ema k ha e en hough o he po-
en ial ad e se e ec s o BPA, he concen a ions de ec ed exceeded he
egula o y limi in se e al samples, and cyclodiBADGE exceeded he
accep able mig a ion le el o 0.05 µg/g s a ed by he B R in mos o
samples analysed. The es ima ed concen a ions o he o he analy es
we e lowe han he exis ing SMLs. Oligome concen a ions anged
om no de ec ed o 1.37 µg/g, mainly, ou esul s sugges ed a low di-
e a y exposu e. Ne e heless, he highes alues co esponded o olig-
ome s, which is o pa icula conce n since some o hem belong o
C ame Class III. These esul s canno be compa ed wi h o he s udies
because o he knowledge o he au ho s no exposu e da a o hese mi-
g an s ha e been p e iously published. A o al die s udy wi h a la ge
panel o oligome s, and u he oxicological s udies would be ecom-
mended o e ine his ough es ima ion.
Table 5
Die a y exposu e mean and (P95) o bisphenol A and BADGE de i a i es in he
Spanish adul popula ion (µg/kg bw pe day).
Sample BADGE .2
H
2
O
BPA BADGE⋅H
2
O.
HCl
CyclodiBADGE
BN 0.333 (0.676) 0.0256
(0.0520)
0.0205
(0.0416)
0.210 (0.426)
CH 0.151(n.a.) 0.0547 (n.a.) 0.00342 (n.a.) 0.4105 (n.a.)
CTO 0.482 (1.16) 0.0567
(0.136)
0.0662 (0.159) 0.520 (1.25)
CAG 0.407 (0.977) 0.0756
(0.182)
0.0851 (0.205) 0.671 (1.61)
CAO 0.482 (1.16) 0.0851
(0.205)
0.104 (0.250) 0.463 (1.11)
SCO 0.492 (1.18) 0.0378
(0.0909)
0.0567 (0.136) 0.416 (1.00)
ME 0.0395 (n.a.) 0.00110 (n.a.) 0.00110 (n.a.) 0.0482 (n.a.)
AC 0.328 (0.666) 0.0359
(0.0728)
0.0308
(0.0624)
0.610 (1.24)
RAV 0.0804
(0.177)
0.00183
(0.00402)
0.00183
(0.00402)
0.00183
(0.00402)
GUIM 0.670 (n.a.) 0.235 (n.a.) 0.0906 (n.a.) 0.163 (n.a.)
TOE 0.0207
(0.0986)
0.000646
(0.00308)
0.00162
(0.00770)
0.00517
(0.0246)
TOT 0.000646
(0.00308)
0.000646
(0.00308)
0.000646
(0.00308)
0.000646
(0.00308)
TOR 0.0898
(0.238)
0.00449
(0.0119)
0.00449
(0.0119)
0.0539 (0.143)
JU 0.233 (0.619) 0.0718
(0.190)
0.0898 (0.238) 0.126 (0.333)
GUIB 0.00453 (n.a.) 0.00453 (n.a.) 0.00453 (n.a.) 0.00453 (n.a.)
n.a.: no a ailable
P. V´
azquez-Lou ei o e al.
Food Packaging and Shel Li e 40 (2023) 101183
9
Funding
The s udy was inancially suppo ed by he Minis e io de Ciencia,
Inno aci´
on y Uni e sidades, by Fondo Eu opeo de Desa ollo Regional
(FEDER), and by Agencia Es a al de In es igaci´
on e .no.
PGC2018–094518-B-I00 “MIGRACOATING” (MICIU/FEDER, UE).
CRediT au ho ship con ibu ion s a emen
P. V´
azquez Lou ei o: In es iga ion, Fo mal analysis, Valida ion,
W i ing – o iginal d a . A. Les ido-Ca dama: In es iga ion, Fo mal
analysis, Valida ion, W i ing – e iew & edi ing. R. Send´
on: Concep-
ualiza ion, Me hodology, W i ing – e iew & edi ing, Supe ision,
P ojec adminis a ion. J. Bus os: Concep ualiza ion, Me hodology,
W i ing – e iew & edi ing. R. Ca iou: W i ing – e iew & edi ing. P.
Pasei o: Concep ualiza ion, Me hodology, W i ing – e iew & edi ing,
Supe ision. A. Rod iguez-Be naldo de Qui ´
os: Concep ualiza ion,
Me hodology, W i ing – o iginal d a , Supe ision, P ojec adminis-
a ion, Funding acquisi ion.
Decla a ion o Compe ing In e es
The au ho s decla e ha hey ha e no known compe ing inancial
in e es s o pe sonal ela ionships ha could ha e appea ed o in luence
he wo k epo ed in his pape .
Da a A ailabili y
No da a was used o he esea ch desc ibed in he a icle.
Acknowledgmen s
Au ho s a e g a e ul o he Minis e io de Ciencia, Inno aci´
on y
Uni e sidades o he P edoc o al ellowship ( e . PRE2019–088195)
awa ded o P.V.L.
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Table 6
Die a y exposu e mean and (P95) o polyes e monome s and oligome s in he Spanish adul popula ion (µg/kg bw pe day).
Sample TPA PA IPA 2TPA+EG (L) 2TPA+BD/MBO+DEG (C) TPA+PG+EG (L) 2NPG+2IPA (C)
LEV 0.0326 (n.a.) 0.00906 (n.a.) 0.00362 (n.a.) 0.0905 (n.a.) 2.03 (n.a.) 0.0905 (n.a.) 0.670 (n.a.)
LE 0.0851 (n.a.) 0.00362 (n.a.) 0.00362 (n.a.) 0.0905 (n.a.) 0.870 (n.a.) 0.435 (n.a.) 0.0453 (n.a.)
GUIB 0.0453 (n.a.) 0.00906 (n.a.) 0.00906 (n.a.) * 2.75 (n.a.) 0.0905 (n.a.) 0.0453 (n.a.)
SCA 0.00189 (0.00455) 0.00189 (0.00455) 0.00189 (0.00455) 0.0472 (0.113) 0.0472 (0.113) 0.0472 (0.113) 0.425 (1.02)
GUIM 0.00906 (n.a.) 0.00906 (n.a.) 0.00362 (n.a.) 0.0905 (n.a.) 0.0905 (n.a.) 0.0905 (n.a.) 0.0453 (n.a.)
TOT 0.000517 (0.00246) 0.00568 (0.02710) 0.000517 (0.00246) 0.0129 (0.0615) 0.0129 (0.0615) 0.0129 (0.0615) 0.00646 (0.0308)
TOR 0.00359 (0.00952) 0.00359 (0.00952) 0.00359 (0.00952) 0.0897 (0.238) 0.0897 (0.238) 0.0897 (0.238) 0.0449 (0.119)
RAV 0.0036 (0.00804) 0.0036 (0.00804) 0.00146 (0.00322) 0.0365 (0.0803) 0.0365 (0.0803) 0.0365 (0.0803) 0.0183 (0.0402)
TOE 0.000517 (0.00246) 0.00192 (0.00616) 0.000517 (0.00246) 0.0129 (0.0615) 0.0129 (0.0615) 0.0129 (0.0615) 0.00646 (0.0308)
JU 0.00359 (0.00952) 0.00359 (0.00952) 0.00359 (0.00952) 0.0897 (0.238) 0.0897 (0.238) 0.0897 (0.238) 0.0449 (0.119)
n.a.: no a ailable
P. V´
azquez-Lou ei o e al.
