DETERMINATION OF ACRYLAMIDE IN COFFEE AND COFFEE PRODUCTS

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1 VI, 2012, ,.... DETERMINATION OF ACRYLAMIDE IN COFFEE AND COFFEE PRODUCTS V. L. Hristova-Bagdasaryan, Zh. A. Tishkova and T. M. Vrabcheva National Centre for Public Health and Analysis So a : (AA) International Agency for Research on Cancer (IARC, 1994) [17] ( 2A). -,. -., 40%. GC-MS, g/kg. (LOD) 40 g/kg, a (LOQ) 100 g/kg %, (RSD) ,5%. -.,, /,. 22, -, 59%. < 100 g/kg 486 g/kg, - < 100 g/kg 887 g/kg, < 100 g/kg 422 g/kg. -. :,,,, GC/MS, :...,,,,.. 15, 1431,.: ; , GSM: , v.hristova@ncpha.government.bg : : : : Summary: Acrylamide (AA) is de ned by the International Agency for Research on Cancer (IARC, 1994) [17] as possibly carcinogenic to humans (Group 2A). Formation of acrylamide in foods is a consequence of the reaction between asparagine and sugars or reactive carbonyls, which occurs during frying or baking goods. Due to the large number of heat treatments, coffee is a potential source of acrylamide. Depending on the age of the population, food habits and preferred way of processing, the contribution of coffee to the total dietary acrylamide exposure can reach nearly 40%. GC-MS method with solid-extraction and derivatization was developed for determination of AA in coffee, coffee substitutes and cocoa. The linear range was g/kg, LOD 40 g/kg, LOQ 100 g/kg. The recovery ranged from 68% to 86% and relative standard deviation (RSD) was between 4.5% and 12.5%, depending on the matrix. The additional SPE-procedure was introduced for elimination of residual staining of the extract due to the matrix. The ratio signal/noise was effectively improved, the interfering components were removed. The method developed was applied to analyze samples of 22 types of coffee, coffee substitutes and cocoa, and a content of AA was found in 59% of the analyzed samples. Acrylamide content in coffee varies from < 100 g/

2 kg to 486 g/kg, in coffe substitutes from < 100 g/kg to 887 g/kg., and in cocoa from < 100 g/kg to 422 g/kg. The results obtained for the content of acrylamide in coffee products correspond to the EU reports for the same kinds of products. Key words: Acrylamide, coffee, coffee products, food contaminants, GC/MS method, SPE Address for correspondence: Chief ass. eng.v. Bagdassarian, PhD, Department Food Contact Materials, National Center for Public Health and Analysis, 15 Akad. Ivan Geshov blvd., Bg 1431 So a, tel: ; , mobile: , v.hristova@ncpha.government.bg Article history: received: revised: accepted: (AA) International Agency for Research on Cancer (IARC, 1994) [17] ( 2A) ,, [28]., - (,.) C 3 H 5 NO. -,,,.,,,,. -, -. - ( ),,, -,, -,. (,.), -., -. - [29]. -, (Roundup).,. (, ) -,,,. - - [6]., -. -,,,, -,,, -,, -., - (2,3- ), (. 1) [6] , EFSA [2], [1]. -, -. -,,, [16].

3 GC-MS - [9, 21, 22, 23], - [10, 18]. LC-MS [18] [4, 8, 14, 25]. -,,, - -,,,, - GC-MS.. -, 7.. -, - :,,,,. -,, -, ( ), ( ),, ( - ), ( ). -, -,,,, -,,,, -. - EFSA - [2]. -,,., - [13, 16, 27] g/day, 39% (31 g/day) [24]., AA - 25 g/kg. Dybing Sanner (2003) [13], 28% 38 g/day 29% 29 g/day g/kg 10 g/kg (Norwegian Food Control Authority, 2002). - Maillard, - [16]. - -, [7, 14, 16, 19, 29]. [12]. Granby Fagt (2004) [15] 2-16 g/l - 10 g/l -, 10 g/day 9 g/day %. P. E. Boon. [11] g/kg, 13%. US Food and Drug Administration (FDA) 6 o 16 g/l [5]., 40%. -, EFSA,, -. - [1]. -, - -, ù (2-BP).

4 E ( - ),,, 2,3- - (2,3-DBP) GC-MS -. 2,3-DBP 2- - (2-BP),., 99%, Sigma-Aldrich; - DISCOVERY DSC-18 (SUPELCO); Supelclean LC-18 SPE Tubes (6 ml/1 g);, Merck;, min 99.5%,, Merck;,, -, Merck;, ACS, 99.0%, Sigma-Aldrich;, 48.3%,, Sigma-Aldrich; %, Merck;, -, erck; n-, SupraSolv,, Merck. : 500 ml - 1 l 200 g ml 48% ml. 1 l. +4º 1. (Na 2 S 2 O 3.5H 2 O), 1. : / n- (1:1) mg/ml g/ml 1 g/ml : - 40 ml 10 ml. (. 2) -, : 0, 50, 100, 200, 500, 1000, ng.. -., (SPE). Agilent Technologies GC-6890N MSD-5975 Inert (EI). 5% -95% - (HP-5MS), 30 m x 0.25 m, 0.25 mm i.d.,,, : - (5 ), ( 6, 1 ), (3 ), - (3 ), (3 ). -. -, : = 1 : 10. -,,. -. (,, - - ). 2 g 2.5 ml. I. 18 ( ) 1 g DISCOVERY DSC-18 (SUPELCO) 50 ml. : 10 ml, -, 5 min ml, 5 min.

5 min ml - DISCOVERY DSC II. SPE ( ) Supelclean LC-18 SPE Tubes (6 ml/1 g) 10 ml 10 ml,,.. 4 ml., SPE -,, ,, - 15 ml - 1 h g : - / - (4 : 1). ( 1) 10 ml, 15 min 310 (rpm) 5000 (rpm) 10 min. - ( 2) 50 ml. : ml,, , ml GC-MS -. GC-MS 5% -95% - (HP-5MS), 30 m x 0.25 m, 0.25 mm i.d., 0.8 ml/min, 15 : 1, 260º, - : 40º ( 1 min);, 20º /min 175º (5 min) 40º /min 280º ( 10 min); MSD 280º ; 1 l. - SCAN MSD. 2-BP 5.58 min. 2-BP NIST -. SIM MSD, - (m/z): 44, 70, 106, BP g/kg. (LOD) - 40 g/kg, a - (LOQ) 100 g/kg.

6 , g/kg, g/kg, % (RSD),% I ± , - 2. < 100* ± < 100* , ± ± ± , - 2. < 100* , - 2. < 100* < 100* , ± , , ± ± < 100* < ± ± < 100* ± II ± < 100* ± ± , ± III ± < 100* ± ± , 4 :,, %:50%. 3,,,,,. * (LOQ): 100 g/kg.

7 , 4-3. <100 g/kg 887 g/kg. < 100 g/kg 486 g/kg, - - < 100 g/kg 887 g/kg, < 100 g/kg 422 g/kg. EFSA [29, 30] ( g/kg) - ( g/kg) %. - -, -, /.. 3 3, -, GC-MS SCAN ( TIC) SIM ( m/z: ) Total Ion Current Time (min) (min). 3a. (SPE) Total Ion Current Time (min) (min). 3. (SPE)

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