determination of acrolein in french fries by soli1

8/13/2019 Determination of Acrolein in French Fries by Soli1

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Determination of acrolein in french fries by solid-phase microextraction

gas chromatography and mass spectrometry

Vanessa Moreira Osrio,

Zenilda de Lourdes Cardeal ,

Departamento de Qumica, ICEx, Universidade ederal de Minas !erais, "venida "ntonio Carlos ##$%, &'$%()(' *elo

+orionte, M!, *rail

"-stract

./e 0r1in2 o0 0oods in t/e /ome can -e a cause o0 indoor pollution due to t/e 0ormation o0 acrolein3 ./e

emission o0 acrolein 0ormed durin2 0r1in2 in so1-ean, corn, canola, sun0lo4er and palm oils 4as studied3 "

!C5M6 met/od /as -een developed to determine acrolein in renc/ 0ries usin2 67ME as t/e samplin2

tec/ni8ue a0ter derivatiation 4it/ $,9:dinitrop/en1l/1draine ;D( ?C 0or $ min a0ter an adsorption time o0 '( min at room temperature3 ./e met/od presented

2ood resolution, repeata-ilit1, detection and 8uanti0ication limits, and linearit1 o0 response3 renc/ 0ries 4ere

prepared in 0ive di00erent oils 4it/ 0our 0r1in2 steps3 ./e results s/o4ed t/at c/an2es in acrolein concentration

occurred a0ter 0r1in2 potatoes in di00erent t1pes o0 oil and at di00erent 0r1in2 c1cles3 7otatoes 0ried in so1-ean oil

contained t/e lo4est concentration o0 acrolein3 6/oestrin2 potatoes contained a lo4er concentration o0 acrolein

t/an potato c/ips and renc/ 0ries, respectivel1, -ecause o0 t/e /i2/er sur0ace5volume ratio3

@e14ords

!C5M6A

67MEA

"croleinA

renc/ 0riesA

6o1-ean oilA

Corn oilA

Canola oilA

6un0lo4er oilA

7alm oil

'3 Introduction

"crolein is a car-on1l compound ;CC= t/at is also Bno4n as acr1lic alde/1de or $:propenal3 "crolein is

introduced dail1 into t/e environment 0rom man1 sources suc/ as automo-ile emissions, ci2arette smoBe,

0orest 0ires, /eated cooBin2 oil, and industrial processes'3"crolein is produced -1 t/e incomplete com-ustion

o0 or2anic material, as 4ell as -1 t/e oxidation o0 atmosp/eric c/emicals suc/ as ',&:-utadiene, a primar1

component o0 motor ve/icle ex/aust3 It can also -e 0ormed -1 t/e oxidation o0 volatile or2anic compounds

released -1 /ome 0urnis/in2s, -uildin2 materials, carpetin2, 4ood 0inis/es, 2lues, ad/esives, and paints$3

"crolein is ver1 toxic via all t/e routes o0 administration and ma1 cause respirator1 and ocular irritation3

Contact 4it/ acrolein ma1 produce necrosis o0 t/e sBin or e1e &3

*ecause o0 its toxicit1, t/e determination o0 acrolein residues in some 0oods, mainl1 0ried 0oods, is important3

"crolein is released -1 0r1in2 0oods3 It is 0ormed -1 t/e de/1dration o0 2l1cerol, 4/ic/ is o-tained 0rom t/e
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/1drol1sis o0 tri2l1cerides3 +o4ever, t/e development o0 anal1tical procedures 0or t/e determination o0 volatile

c/emicals suc/ as acrolein in 0att1 samples is a c/allen2e -ecause it is /i2/l1 volatile, /i2/l1 reactive, and is

capa-le o0 sel0:pol1meriation 93

@no4n met/ods 0or determinin2 car-on1l compounds re8uire a derivatiation step t/at usuall1 involves a2ents

suc/ as >,>:dimet/1l:',&:c1clo/exanedione,


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restaurants, and 0ood industries 4ere simulated3 ./ere0ore, t/e present stud1 sou2/t to develop an anal1tical

met/od 0or determination o0 acrolein derivatied 4it/ $39:D min3 "0ter 0r1in2, eac/ oil4as cooled and stored 0or t/e next re:use until 0our 0r1in2 c1cles 4ere completed3

$3&3 6tatistical met/ods o0 optimiation

.o optimie t/e anal1sis met/od, a stud1 o0 t/e varia-les considered si2ni0icant 0or t/e experiment 4as

conducted usin2 a 0actorial desi2n stud1in2 $9varia-les extraction time, '( min ;= and 9( min ;N=A

temperature, &( ?C ;= and >( ?C ;N=A concentration o0 sodium c/loride ;C minA temperature, 9( ?CA salt concentration, >KA desorption time, %> s3 ./e 7areto c/art

4as dra4n 0or anal1sis o0 t/e si2ni0icant varia-les so t/at t/e -est 4orBin2 conditions 0or per0ormin2 t/e

anal1sis could -e c/osen3 6ome tests 4ere conducted to validate t/e met/od in accordance 4it/ t/e2uidelines o0 t/e Eurac/em '))F '#0or t/e validation o0 anal1tical met/ods3 ./e parameters studied 4ere

linearit1, detection limit, 8uanti0ication limit, and precision3

$3&3'3 67ME extraction met/od

./e solid p/ase microextraction ;67ME= 4as per0ormed 4it/ a manual /older 4it/ F>:Hm pol1acr1late ;7"=

;purc/ased 0rom 6upelco, *elle0onte, 7", U6"=3 7rior to use, t/e 0i-ers 4ere conditioned accordin2 to t/e

manu0acturers instructions3 ./e 0i-er 4as exposed to t/e sample 0or a suita-le period ;'( min= at room

temperature and introduced into t/e !C inector ;set at $>( ?C and runnin2 in t/e splitless mode= 0or $ min3

or t/e anal1sis o0 potatoes -1 !C5M6, '&3(( 2 o0 potato c/ips 4ere 4ei2/ed and placed in a -eaBer

containin2 F(3( mL o0 a8ueous D


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!C5M6 anal1ses 4ere conducted on a .race !C Ultra c/romato2rap/ e8uipped 4it/ a 7OL"JI6 Q model ion

trap mass spectrometer ;./ermo Electron, 6an Pose, C"=3 "n +7:>M6 ;"2ilent, 6anta Clara, C"= capillar1

column ;&( m (3$> mm id (3$> Hm 0ilm= containin2 >K dip/en1l and )>K dimet/1lpol1siloxane 4as used3

./e inlet 4as adusted to operate in t/e splitless mode 0or $ min at a temperature o0 $>( ?C3 ./e temperature

o0 t/e oven 4as pro2rammed as 0ollo4s '$( ?C ;/oldin2 time, $ min= 4it/ an increment o0 '( ?C5min up to

$)( ?C ;/oldin2 time, > min=, terminatin2 4it/ an increase o0 '( ?C5min up to &(( ?C 0or $ min3 ./e total run

time 4as $% min, and /elium 4as used as t/e carrier 2as at a constant 0lo4 o0 '3> mL5min3 ./e 0ollo4in2

parameters 4ere used 0or operatin2 t/e mass spectrometer electron ioniation at %( eV, 0ull scan mode 4it/ a

mass ran2e o0 >(#>( m5z, and a source temperature o0 $(( ?C3

$3>3 att1 acids anal1sis

./e 0att1 acid compositions o0 t/e oils 4ere determined as t/e met/1l esters -1 !C5ID3 "nal1ses 4ere

per0ormed on an +7>F)( !as C/romato2rap/ e8uipped 4it/ a 0lame ioniation detector3 " Econocap

car-o4ax column ;"lltec/= &( m (3&$ mm (3$( Hm 4as used3 ./e temperature pro2ram -e2an 4it/ t/e

oven temperature at '$( ?C 0or ' minA t/e oven 4as /eated at a rate o0 % ?C5min to $9( ?C and /eld 0or & min3

./e 0lo4 rate o0 t/e /1dro2en carrier 2as 4as $ mL5min3 ./e inector 4as maintained at $>( ?C in split mode at

t/e ratio o0 '>(, and t/e temperature o0 t/e detector 4as $>( ?C3 ./e identi0ication o0 peaBs 4as ac/ieved -1comparison 4it/ a 6upelco&% ;6upelco= 0att1 acid met/1l ester standard mix3

&3 Jesults and discussion

" c/romato2ram and mass spectrum o0 t/e acrolein standard are presented ini23 ',demonstratin2 t/e 0act

t/at t/e met/od is selective and e00icient3 " $90actorial desi2n ;conditions and parameters studied are

descri-ed in 6ection$=4as proposed to optimie t/e 67ME parameters3 " 7aretos plot 4as constructed ; i23

$= to determine t/e most si2ni0icant e00ects 4it/ a con0idence interval o0 )>K3 ./is plot s/o4s t/at t/e

extraction temperature ;*= 4as si2ni0icant at t/e lo4est temperature utilied and t/e salt concentration ;C= and

desorption time ;D= 4ere si2ni0icant at t/e /i2/est values, considerin2 a )>K con0idence level3


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i23 '3

!C5M6 c/romato2ram in t/e ull5scan mode and mass spectrum at m5z$ correspondin2 to an acrolein:D ?C and '(K


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*ased on t/is result, t/e extraction time c/osen 4as '( min, 4/ic/ permitted 0aster anal1ses3 ./e desorption

time and C


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Concentration o0 acrolein in renc/:0ried potatoes 0ried in so1-ean, canola, sun0lo4er, corn and palm oil3 Eac/ oil 4as

reused in 0our 0r1in2 c1cles3

i2ure options

./e results s/o4 t/at t/e level o0 acrolein in potatoes 0ried in so1-ean oil /ad an avera2e concentration o0

'399 n252, 4it/ a ran2e 0rom (3#F to $3)) n2523 In addition, t/e concentration o0 acrolein in t/e 0ried potatoes

si2ni0icantl1 decreased 4it/ num-er o0 times t/at t/e so1-ean oil 4as rec1cled3

Por2e et al3'%concluded t/at t/e potatoes a-sor-ed a smaller 8uantit1 o0 so1-ean oil t/an sun0lo4er and

corn oils3 6o1-ean oil /as a lar2er amount o0 saturated 0att1 acids, 4/ic/ decreases t/e a-sorption -1 t/e

0ood 'F3 ./ese 0actors ma1 /ave contri-uted to t/e values 0ound in t/is stud1, since t/e a-sorption o0 a

smaller amount o0 oil can a00ect t/e amount o0 acrolein retained in 0ood3 "not/er 0actor t/at explains t/e result

o-tained in t/is stud1 0or so1-ean oil is t/at t/e amount o0 2l1cerol decreases 4it/ t/e reuse o0 oil, t/ere-1

decreasin2 t/e acrolein concentration3

./e avera2e concentration o0 acrolein in potatoes 0ried in sun0lo4er oil 4as &3$> n252 4it/ a ran2e 0rom $3%F to

93(( n2523 "n avera2e concentration o0 93(F n252 4it/ a ran2e 0rom $3$> to 93F> n252 4as o-served 0or t/e

potatoes 0ried in corn oilA and a mean o0 &3%& n252 4it/ a ran2e 0rom '3)% to 939% n252 4as o-tained 0or t/e

potatoes 0ried in canola oil3

In t/e case o0 t/e sun0lo4er, canola and corn oils, t/e concentration o0 acrolein remained almost constant 0or

t/e potatoes 0ried in t/e t/ree t1pes o0 oil durin2 t/e 0our 0r1in2 c1cles3 +o4ever, a si2ni0icant increase in t/e

acrolein concentration occurred in t/e last 0r1in2 step in t/e case o0 t/e sun0lo4er oil, 4/ile a decrease

occurred in t/e second and 0ourt/ 0r1in2 steps in t/e canola and corn oils, respectivel13 ./e acrolein

concentration 4as /i2/er in t/e potatoes 0ried in t/e t/ree t1pes o0 oil mentioned a-ove t/an 4/en so1-ean oil

4as used3 ./e concentrations o0 unsaturated 0att1 acids presented in.a-le 's/o4 t/at sun0lo4er, canola and

corn oils contain /i2/er concentrations o0 unsaturated 0att1 acids t/an does so1-ean oil3 ./is 0actor 4ould lead

to t/e a-sorption o0 a lar2er 8uantit1 o0 oil -1 t/e 0ood3 ./is 0act explains 4/1 t/e acrolein concentrations 0ound

in potatoes 0ried in sun0lo4er, canola and corn oils are /i2/er t/an t/ose 0ound in potatoes 0ried in so1-ean oil3

.a-le '3

Jan2e 0or unsaturated 0att1 acid composition and viscosit1 values o0 samples o0 ve2eta-le oils ;so1-ean, canola, corn,

sun0lo4er and palm oil=3

Unsaturated fatty acid Soybean Canola Corn Sunflower Palm

Values expressed in % p/p of methyl esters

C18:1 22.07 56.72 !.6" 28.12 6.72

C18:2 5.70 2.1 !7."1 58.66 28.10

C18: 6.1 8.!7 1.6 0.52 2.5!

#otal 82.71 88.50 8!.2 87.0 67.6

Values expressed in cP

$iscosity 5.60 65.10 56.!0 50.00 "".50

.a-le options

./e content o0 unsaturated 0att1 acids is /i2/er in sun0lo4er oil ;F%K= t/an in corn oil ;F9K=, as is s/o4n

in.a-le '3 ./is 0act does not usti01 t/e /i2/er concentration o0 acrolein in t/e potatoes 0ried in corn oil3 ./e

temperature durin2 t/e 0r1in2 process is anot/er 0actor t/at ma1 /ave a00ected t/e results o-tained 0or t/ese

t4o t1pes o0 oil3

In a stud1 conducted -1 7oo:De'),t/e a-sorption o0 t/e oil -1 0ood 4as not directl1 related to t/e num-er

o0 times in 4/ic/ t/e oil 4as re:used, -ut 4as a00ected -1 t/e 0act t/at temperature c/an2es durin2 t/e 0r1in2

process ma1 a00ect t/e a-sorption o0 oil -1 0ood3

6mall variations in temperature 4ere o-served durin2 t/e experiments, 4/ic/ ma1 explain t/e 0luctuation in

acrolein concentration o-served in potatoes 0ried 4it/ canola, corn, and palm oils3 inall1, t/e results 0or t/e

anal1sis o0 acrolein in potatoes 0ried in palm oil /ad an avera2e concentration o0 '3)& n252, 4it/ a ran2e 0rom
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'3(F to $3(# n2523 ./e acrolein concentration 4as similar t/rou2/out almost all t/e 0r1in2 c1cles3 ./e 0actor t/at

usti0ies t/e di00erent concentrations o0 acrolein encountered is t/e same as t/at mentioned a-ove 0or t/e ot/er

oilsA /ence, c/an2es in temperature durin2 t/e 0r1in2 process can -e expected to cause a c/an2e in t/e

a-sorption o0 oil -1 t/e 0ood3

./e potatoes 0ried in palm oil contained lo4er concentrations o0 acrolein a0ter t/e 0irst 0r1in2 c1cle ;i23 &=3

"ccordin2 to 7aul and Mittal$(,several 0actors a00ect t/e penetration o0 oil into t/e 0ood, one -ein2 t/eviscosit1 o0 t/e 0r1in2 oil3 7alm oil presented t/e /i2/est viscosit1 o0 t/e oils studied3 ./is 0actor ma1 /ave

contri-uted to t/e 0indin2 t/at t/e potatoes 0ried in palm oil contained a lo4er concentration o0 acrolein a0ter t/e

0irst 0r1in2 c1cle3

./e concentration o0 acrolein in commercial potato sticBs ;renc/ 0ries= purc/ased in a 0ast 0ood restaurant,

s/oestrin2 potatoes 0or sand4ic/es, and potato c/ips 4ere similarl1 determined3 ./e results are represented

ini23 93 ./e concentrations o0 acrolein in potato c/ips and s/oestrin2 potatoes 4ere muc/ lo4er t/an t/at

o-served in renc/ 0ries3 One 0actor t/at explains t/is di00erence is t/at t/e sur0ace5volume ratio is muc/ /i2/er

0or potato c/ips and s/oestrin2 potatoes t/an 0or renc/ 0ries3 "ccordin2 to 7aul and Mittal$(, t/e

sur0ace5volume ratio o0 0ood in contact 4it/ t/e 0r1in2 oil is an important contri-utin2 0actor 0or determinin2 t/e

amount o0 oil a-sor-ed -1 0ood3 ./e a-sorption o0 t/e oil -1 0ood depends mainl1 on t/e distance 0rom t/e

center to t/e sur0ace o0 0oods suc/ as t/e potato c/ips and renc/ 0ries used in t/ese experiments3

i23 93

Concentration o0 acrolein in commercial potatoes3

i2ure options

93 Conclusions

./is 4orB descri-es an alternative 67ME:!C5M6 met/od 0or t/e determination o0 acrolein in 0ried potatoes3

./is procedure 4as validated and 0ound to -e precise, sensitive and linear in t/e ran2e o0 interest3 67ME

represents a 2ood alternative met/od 0or t/e 8uantitative anal1sis o0 acrolein in 0ried 0oods3 ./e acrolein

concentration varied 4it/ t/e t1pe o0 oil emplo1ed 0or 0r1in2 and 4it/ t/e num-er o0 times in 4/ic/ t/e oil 4as

reused3 +o4ever, t/e values 4ere -elo4 t/e limit recommended -1 t/e Rorld +ealt/ Or2aniation ;$(($=,

4/ic/ speci0ies t/at t/e acrolein concentration s/ould -e a maximum o0 9( H252 in 0oods
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determination of acrolein in french fries by soli1

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