Translation Series No Changes in rape-seed oil under severe heat treatment conditions. by M. Kasperek and B. Leszkiewicz

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1 I^RCHIVES 4 FISHERIES AND MARINE SERVICE Translation Series No Changes in rape-seed oil under severe heat treatment conditions by M. Kasperek and B. Leszkiewicz Original title: Zmiany w oleju rzepakowym w warunkach ostrej obrobki cieplnej From: Zesz. Nauk. Akad. Ekon. Poznaniu 62(Ser. 1): 25-30, 1975 Translated by the Translation Bureau (NWJ) Multilingual Services Division Department of the Secretary of State of Canada Department of the Environment Fisheries and Marine Service Halifax Laboratory Ualifax, N.S i 9 pages typescript

2 DEPARTMENT OF THE SECRETARY OF STATE TRANSLATION BUREAU MULTILIMGUAL SERVICES DIVISION ieeee- CANADA SECRÉTARIAT D'ÉTAT BUREAU DES TRADUCTIONS DIVISION DES SERVICES MULTILINGUES F Li 3 TRANSLATED FROM - TRADUCTION DE Polish mm- EN English AUTHOR - AUTEUR Kasperek Marian, Leszkiewicz Barbara TITLE IN ENGLISH - TITRE ANGLAIS Changes in rape4rseed oil under severe heat treatment conditions TITLE IN FOREIGN LANGUAGE (TRANSLITERATE FOREIGN CHARACTERS) TITRE EN LANGUE ÉTRANGÈRE (TRANSCRIRE EN CARACTÈRES ROMAINS) Zmiany w olejusrzepakowym w warunkach ostrej obrobki ciepinej REFERENCE IN FOREIGN LANGUAGE (NAME OF BOOK OR PUBLICATION) IN FULL. TRANSLITERATE FOREIGN CHARACTERS. RÉFÉRENCE EN LANGUE ÉTRANGÈRE (NOM DU LIVRE OU PUBLICATION), AU COMPLET, TRANSCRIRE EN CARACTÈRES ROMAINS. Zesz. Nauk. Akad. Ekon. w Poznaniu REFERENCE IN ENGLISH - RÉFÉRENCE EN ANGLAIS Scientific publications of the School of Economics in poznan PUBLISHER - ÉDITEUR Not given PLACE OF PUBLICATION LIEU DE PUBLICATION Poland YEAR ANNÉE 1975 DATE OF PUBLICATION DATE DE PUBLICATION VOLUME 62 ISSUE NO. NUMÉRO Ser. PAGE NUMBERS IN ORIGINAL NUMÉROS DES PAGES DANS L'ORI GINAL NUMBER OF TYPED PAGES NOMBRE DE PAGES DACTYLOGRAPHIÉES 9. REQUESTING DEPARTMENT Environment TRANSLATION BUREAU NO MINISTÉRE-CLIENT NOTRE DOSSIER N BRANCH OR DIVISION DIRECTION OU DIVISION PERSON REQUESTING DEMANDÉ PAR pi_sheries Scientific Inf. -& Publications Branut Dr. R.G. Ackman TRANSLATOR (INITIALS) TRADUCTEUR (INITIALES) YOUR NUMBER VOTRE DOSSIER N Dec DATE OF REQUEST MU.fr. ' (5 DATE DE LA DEMANDE SOS (REV. 2/88) ; lar.dnr.oiln only ce> I: V NON :3 EE: r.e [rdor.r.i)o;1 boulornont UJ

3 Secretary Secrétariat of State d'^tat TRANSLATION BUREAU MULTILINGUAL SERVICES DIVISION BUREAU DES TRADUCTIONS DIVISION DES SERVICES MULTILINGUES Fd m#3q43 CLIENT ^ S N0. NO DU CLIENi BUREAU NO. NO DU DUREAU DEPARTMEN7 MINISTERE Environment LANGUAGE LANGUE DI VISION/ LIRA NCH DIVISION/DIRECTION Fisheries ^cientific inf.& Publicaions aranc TRANSLATOR(INIf1ALS) TRADUCTEUR (INITIALES) polish N.W.J. Cf TV VILLE Halifax ' N. S FEB Zesz. Nauk. - Akad. Ekon. w poznaniu, Ser. 1 (Scientific Publications - School of Economics in Poznan, Ser. 1), 1975, vol.'62, pp CHANGES IN RAPE-SEED OIL UNDER SEVERE HEAT TREATId1ENT CONDITIONS by jr or -marv5eatim,19 m'orm ^: iâ1, vniy N: Rw ^! SEI Kasperek Marian and Leszkiewicz Barbara^,,,,_,,, j_.in snulv;,; According to some authors' viewsel-3), rape-seed a^ 25 oil fed to animals causes considerable changes in their internal organs. It was believed in the past that the noxiousness of rape-seed oil was caused by erucic acid contained in it. This, however, has not been confirmed E41. The observations of the noxious effect of heated rape-seed oil [5] on animals led us to undertake the task of examining the changes in rape-seed oil that occur during thermal. treatment of it. ^ Numbers in the right-hand margin indicate the correspon - ding pages in the original. SEC 5-25T (6/76)

4 2 The main objective of our study was to determine the changes in rape-seed oil that occur under the condition â of severe thermal treatment, with particular attention given to the stereo-isomerising changes. -Experiment The sapples of raw rape-seed oil, refined rape-seed oil and hardened fat, obtained from Oil Producing Factory in Krusgwica, were employed for the experiment. The description of these products was given in our previous paper [ 3]. The samples placed in glass containers (the containers were 11 cm in diameter, the layer of oil was 3 cm deep) were heated at a temperature of 200±5 C, under normal air conditions. The heating treatment was conducted for 1 hour daily for the duration of 6 days. Between the treatments the samples were kept at room temperature. After each treatment two samples were taken out and examined. The research method was as followa: -- a determination or the number of isolated bonds 'trams' by spectrophotometry under infra-red radiationl7j. The determination was conducted with a specord 1R 71 spectrophotometer in the carbon tetrachloride solution; samples that did not undergo thermal treatment served as a standard. -- a quantitative analysis of fatty acids by means of gas chromatography; the determination was conducted with

5 3 a'varian' apparatus; the distribution was achieved by employing a glass column of cm in length and with an inside diameter of 2 mm, filled with Chromosorb ;Y and a PEGA carrier (10 %) ; temperature of the column was 195 C and the flow rate of the carrier-gas (nitrogen) was 40 cm 3 min.; --- a determination of the refractive index; --- a test on thiobarbituric acid, by means of the alkaline hydrolysis r 81; --- a determination of peroxy compounds. Discussion of the results 26 The results of the experiment are presented in Table 1 and in figures 1-4. The data provided in Table 1 show that the severe thermal treatment of raw rape-seed oil (I) and refined rape-seed oil (II) increases their content of saturated fatty acids and mono-unsaturated fatty acids and, at the same time, decreases their content of di- and tri-urisaturated fatty acids. Flowever, no increase in the amount of mono-unsaturated fatty acids was observed in the hardened fat (III); there was even a decrease in the amount of G18^1. A considerable increase in the fraction 0 CGG:1 was observed in tyle samples I and II. It is particula.rly significant, that prior to the thermal treatrpent, the content of the fraction *CG2. 2 in these samples was much

6 4 too low to attribute the increase of c 22:1 acids to hydrogenation. Further research is essential to explain this phenomenon. A comparison between the content of particular fractions of fatty acids in the samples I, 11, 111, prior to the thermal treatment (Table 1), shows that the refining process affects their levels only a little; the process of hardening occurs mainly at the expense of the fractions C 22:1 018:2' and 0 and is accompanied 188 by the increase in, at first, fraction c and then 18:1 fractions and 0 16:0 018:0 o ocoomix Rys.l. Zawartoid izomerdw ntrans" kwastiw tauszozowych w oleju rzepakowym ogrzewanym w temperaturze I - olej surowy, II - olej reinowany, III - thiszcz utwar-. dzony 1. Fig. 1. The content or isomers 'trans' of fatty acids in rape-seed oil heated at a temperature of 200 C. 1-raw rape-seed oil, II-refined rape-seed oil; III-hardened. fat.

7 play a 5 Isomeric changes are presented in Fig.l. As can be seen from the diagrams, thermal treatment causes a considerable increase in the amount of isomers 'trams' in the samples I and II, while in the samples III their content.fluctuates and, finally, decreases a little after the treatment. The quantitative changes in isomers 'trans' (Fig.1), as compared with the quantitative changes in particular fractions (Table 1), show that the acids C 221 considerable role in isomerization and, thus, probably in the formation of brassidic acid which is harmful to human health. The comparison in pig.1 between the initial quantities (the samples II and III before the thermal treatment) shows that the process of refining, and particularly, that of hardening, cause a significant increase in isomers 'trans'. The content of these stereo-isomers in the samples, prior to the thermal treatment, was as follows: in raw oil - 6%, in refined oil % and in hardened fat % of the total quantity of fatty acids. The courses of further changes were determined on the basis of the tests with thiobarbituric acid, of L.Lea value, and of refractive index. Irregular but conltant - increase in the value of the tests with thiobarbituric acid with the increase of heating time (Fig. 2) shows a progresive process or aging of the examined fats.

8 Table 1 The quantitative changes of fatty acids in rape-seed oil during the heating at a temperature of 200 C (in the per-cent of the total content of fatty acids) -. Ilebolowe Esiany kwaaber tluearlsowioh olele rzepakowego w «ante 06=e:weals w.temeratuize (w prooeeteah oelaej sawartoboi kweebw tluesozoryoh) a b 1 a j, 1 1 Oloj eutory (I) Olej rafinoweiny.(ii). =oat= utwardsony (III) e." :. Cep.» ogrrew icaia. w..minut.ao IL. e. : 1. GO " * C 12, 0 61a4y blady blear 61a 1i nady blady blady 61ady 61a6y 61a4y blidy blady biady 61ady. 0,06 0,07 0,06 0,07 0,09. 0,11 0,,e1 61.6I blear blady blady dlady 61a4y blady blady 41e élady hludy ad7 0,10 0,11 0, ,17,4 00 0,15 C 14,0 " 1 6, 0 2,48. 2, ,68 2,70 2,74 3,05 2,50 2,73 2,76 2,92 " 3,20 3,51 5,70 I 4,96 ' 5,13 5,27 5,56.5;59 6,04 6,93 0, 6, 1 0,24 0,25 0,24 0,24 0,26 0,26 0,30 0,25 0,25 0,23 :0,26 0,26 0,28 0,213 0,54 0,53 0,50 0;51 0,52.0,50 0, :3 blady blady 61a4y blady blady 61a67 élady eady 61a4y bleep 61ady blady bley ilady 0,0: 0,0 0,0 0,0 0,0 0, 0; 9,0.:., 0,75 0, ,95 1,00 0,80 0,80.0,84 0,93 1,00 1,12 1,15 3,49 coo 5, ,80 5,84 3, ,30 10,42 10,69 10,92 10,95 10,30 10,40 10, ,99 11,09 11,20 29,54 29ii3 29,17 20,05 20,75 20,56 20,20 C18:2 15,07 12,98 12,30 12,15 12,02 11,51 11,00 1 3,3 8 12:05 12,31 11, ,07 10,03 4,70 4,50 4,46 4, ;97 5,09 0w, 9,70 9,22 8,3 0 7, ,02 5,40 9,00 8,00 7,50. 6,87 6,20 5, ,1D ' 403. leo 1,00 1,76.1,67 1,56 I ,32 0,40 0,35 0,25.0, ,70 0,65 '0, , 60 0,60 l ' i * 1;40 1.,43 1,48 1,54 1,61 1, : ,70 6,75 6,62 7,16 7,24 7,34 7,25 6,75 7,01 7, ,06 7;07 7,05 7,00 7, , ,41 7,40 7,48 C20:1 020, , , 29 0,30 0, ; ,26 0,26 0,23 0,0 0,0 0, 0 0,0 fi,o 0,0. 0,0 022, 1 5>01 55,92 56,96 57,62 58,52 59,22 60,00 55,35 56,16-57,03 57,78 50,63 59,32 60,27 45,80 43,86 45,90.46, ,b7 45,84 022:2 0, ,51 0,45 0,5 0 Me 070 0,70 0,68.0,67 0,70 0,63 0,66 0,0 0,0 0,0 0,0 0,0 0,0. 0,0. -, : fatty acids; 2. raw rape-seed oil; 3. refined rape-seed oil; 4. liardened fat; 5. time of heating in minutes. 0)

9 28 n4 W W M 2 WO tki Rys.2. Wertogei prdby ziwasem tiobarbiturowym oleju rzepakowego ogrzewanego w temperaturze , wyraone jakn ekstynkcja roztworu o grubosci warstwy 5 cm (oznaczepla jak na rys. 1) Fig. 2. The results of the test of thiobarbituric acid and rape-seed oil heated at a temperature of , expressed as the extinction of the solution layer of 5 cm in depth, ( designations as in Fig.1 ) woo 11.1e90 veso 2-7 ;481: a^ el x-"..* eit) W U0 e Lb Rys.3. Wartogei wspdiczynnika zalamania gwiatla oleju rzepakowego ogrzewanego w ter» peraturze (Oznaczenia jak:na rys.1) Fig 3. The values of th-e refractive index of rape-seed oil heated at a temperature of 200QC, (designations as in Fig. 1). t (.4

10 8 In the course of the increase in the length of heating time, a gradual increase of refractive index was observed (rfig.3), caused most likely by aprogressive process of polimerization of fatty acids. This is in accordance with Sal.zer and ;^rurziber' s results [9j, who observed that about 50 % of fatty acids in heated oil' are pol^.merized. ^^ ^:^,:, -,trj- Ryo.. ^7^tosci liczby n. dt1en- Y.or;e j(i,^ ea) o1eju rzep--li_oercpo o^, r^ nace ti: t^ a_ crnter e 200^C J-,'c n^. 1"S3. 1) Fig. 4. The values of the peroxy number ( L. Lea) of rape-seed oil heated at a temperature of 200 C, ( designations as in Fib.l). The content of peroxy compounds was increasing 29 up to the third and fourth hour of heatin6. vurir.6 further thermal treatment, the level of' peroxxcles decreased; this was connected with the secoiiduiy conversion

11 of these compounds. Relatively low L.Lea values and the results of TBA tests, along with simultaneous considerable increase of the refractive index, make it possible to conclude that, in the conditions of severe thermal treatment, the processes of pold_aerization and isomerism dominate over oxidative changes. S u r y A study was carried ont oi.the changes in rapeseed oil - raw, refined and h..rdened fat - subjected to severe thermal - treatment...in raw and refined oils a marked increase was observed in saturated fatty acids, this being e.cco:-...panied by a drop in di- and tri-unsaturated acids. The severe thermal treatment causes an extensive cis-"=ans isomerism and polymerisation. These two processes were found to dominate over oxidative changes. Refining was found to affect very little the fatty- acids composition - and hydrogenation was accomplished at the cost of the fractions 022:1. and 0 with en increase in the fractions C C 18:1' 18:0 and 0 16:0. 18:2 Refining and particularly hardening result in a considerable increase of isomers ntranen. P 1 C27 [3 ] '.[4 ] 53. [6 ] Thorne Pijpen, nr ( 19 S.Zalews wioz, 225 (1572). H.Ziombe 413 ( 1970). G.Rocque Sauk Roln., nr Bibliography Literatur a sson., J.3.Gottenbos, P.1.. Van R.O. V 1 e Zeszyty Problemowe Post. Nauk.Roln., 70).. ki, P...Br_zozowska, Z.Ole 61ric- B ar tnik; Roczn. Techn. i Cheaii Zywn. 22(2), k 1. ; Zeszyty Probleuowe Post. Nauk. Rom., nr 91, l in,.r. C 1 91, 403 (1970). k i uz an: Zeszyty Problemowe Post. S. Zieml a T..Opuszyliska; M.Rusieok a : Zeszyty Problemowe Nauk Roln., ;Jr 91-, 425 (1970). ' LI.Kasperek eszki.ewioz: ZeSzyty naukowe AS w Poznaniu,. S-e'ria 1, nr 58, 59 (1974). Ui7 K.Modzelewska, A.Jaknboviaki:Tiuszcze daine nr 10, 136 (1966). [133. T. Witae: Zeszyty rankowe 17T:1 w Szczecinie nr 4, (1973). [9 ] II.J. Selzer, 3. Wurziger : Pette Seifen Anstrichnittel, 12, 705 (1971).