This article was downloaded by: [University of Windsor] On: 12 November 2014, At: 16:55 Publisher: Taylor & Francis Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Food Additives & Contaminants: Part B: Surveillance Publication details, including instructions for authors and subscription information: http://www.tandfonline.com/loi/tfab20
A survey of levels of ethyl carbamate in alcoholic beverages in 2009–2012, Hebei Province, China a
b
Yinping Liu , Shuhui Wang & Ping Hu
b
a
Hebei Provincial Center for Disease Control and Prevention , Shijiazhuang , 050021 , People's Republic of China b
Shijiazhuang Center for Disease Control and Prevention , Shijiazhuang , 050019 , People's Republic of China Accepted author version posted online: 10 May 2013.Published online: 21 Jun 2013.
To cite this article: Yinping Liu , Shuhui Wang & Ping Hu (2013) A survey of levels of ethyl carbamate in alcoholic beverages in 2009–2012, Hebei Province, China, Food Additives & Contaminants: Part B: Surveillance, 6:3, 214-217, DOI: 10.1080/19393210.2013.803162 To link to this article: http://dx.doi.org/10.1080/19393210.2013.803162
PLEASE SCROLL DOWN FOR ARTICLE Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and should be independently verified with primary sources of information. Taylor and Francis shall not be liable for any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of the Content. This article may be used for research, teaching, and private study purposes. Any substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http:// www.tandfonline.com/page/terms-and-conditions
Food Additives & Contaminants: Part B, 2013 Vol. 6, No. 3, 214–217, http://dx.doi.org/10.1080/19393210.2013.803162
A survey of levels of ethyl carbamate in alcoholic beverages in 2009–2012, Hebei Province, China Yinping Liua, Shuhui Wangb and Ping Hub* a Hebei Provincial Center for Disease Control and Prevention, Shijiazhuang 050021, People’s Republic of China; bShijiazhuang Center for Disease Control and Prevention, Shijiazhuang 050019, People’s Republic of China
Downloaded by [University of Windsor] at 16:55 12 November 2014
(Received 22 December 2012; final version received 3 May 2013) Results of a survey of levels of ethyl carbamate (EC) (urethane) in alcoholic beverages carried out in four successive years from 2009 to 2012 by gas chromatography-mass spectrometry (GC/MS) are presented. The beverages were purchased for sampling from Hebei Province of China, including eight main areas of production. The samples comprised wines (n = 212), grain spirits (n = 143) and wine sauces (n = 164). The data show that the average EC content in these kinds of alcoholic beverages remains nearly constant over the years. The results provide valuable data for food authorities to establish maximum limits for EC in China. Keywords: ethyl carbamate; alcoholic beverages; GC/MS; variation tendency
Introduction Ethyl carbamate (EC) is ethyl ester of carbamic acid and has widespread occurrence in fermented foods and beverages, with levels ranging from nanograms per litre to milligrams per litre (Battaglia et al. 1990; Uthurry et al. 2004; Lachenmeier et al. 2005, 2009; Susana et al. 2005; Park et al. 2009). EC is genotoxic and carcinogenic, and thus a potential carcinogenic risk to humans (Beland et al. 2005). It has been classified as a group 2A carcinogen, i.e. “probably carcinogenic to humans,” by the World Health Organization’s International Agency for Research on Cancer (2007). Since alcoholic drinks are considered as a source of ethyl carbamate, the issue of EC in alcoholic beverages has attracted a great deal of attention in many countries. JECFA (Joint FAO/WHO Expert Committee on Food Additives) estimated a dietary exposure of 17 ng/kg b.w. per day (Food and Agriculture Organisation of the United Nations/World Health Organisation 2006). Main alcoholic beverages consumed in Hebei are wines, grain spirits and wine sauces, so this surveillance focused on EC in these alcoholic beverages from 2009 to 2012. It aimed to search for variation tendency and to provide data for authorities for risk assessment and evaluate establishment of maximum limits for EC in China.
Materials and methods Samples Samples were collected at local markets from eight areas (Shijiazhuang, Baoding, Handan, Qinhuangdao, Langfang, Zhangjiakou, Xingtai and Cangzhou) in the *Corresponding author. Email: [email protected] © 2013 Taylor & Francis
Hebei Province, China. All were domestic alcoholic beverages. The total number of investigated samples consisted of 212 wines and 164 wine sauces (years 2009–2012) and 143 grain spirits (years 2009–2011). No grain spirits were sampled in 2012. Chemicals All solvents were high-pressure liquid chromatography (HPLC)-grade and purchased from J.T. Baker (Philipsburg, CA, USA). The CLE diatomaceous earth columns were provide by Hangzhou Fuyu Technology Service Company Limited (Hangzhou, China). The EC standard (99%) was from Sigma-Aldrich (Madrid, Spain) and the d5-EC internal standard (IS, 99%) was from Cambridge Isotope Laboratory (Andover, MA, USA). Chemical analysis Sample analysis was performed following the procedure described in a previous study (Liu et al. 2011). Briefly, 2.0-g sample was grounded with a known amount of IS, and then subjected to a CLE column. After an equilibration time of 15 min, the analytes were extracted using 10 ml of ethyl ether. The eluate was reduced to dryness under gentle nitrogen gas and re-dissolved in methanol to 1 ml before injection into the gas chromatography-mass spectrometry (GC-MS). A Thermo Trace-GC with an ultra-DSQ mass spectrometer (Thermo Fisher Scientific Inc., Waltham, MA, USA) equipped with A HP-Innowax capillary column (30 m × 0.25 mm × 0.25 µm, Agilent Technologies, Santa Clara, CA, USA) was used for the separation and determination of EC in the extracts.
Food Additives & Contaminants: Part B
215
Table 1. Recoveries and relative standard deviations (RSDs) for EC in wine sauce. Determined times
Spiking level (µg kg−1)
Determined result (µg kg−1)
Recovery (%)
Average recovery (%)
RSDs (%)
8 8 8 50 50 50 200 200 200
6.0 6.3 5.7 46.7 45.6 43.9 189 191 216
75.1 78.9 70.7 93.4 91.2 87.8 94.5 95.5 108.0
74.9
5.4
90.8
3.1
99.3
7.6
Downloaded by [University of Windsor] at 16:55 12 November 2014
1 2 3 1 2 3 1 2 3
Column temperature was held at 60°C for 3 min., then programmed at a rate of 8°C min−1 to 160°C, with a postrun temperature of 240°C for 5 min. Ion source and transfer line temperatures were 230°C and 250°C, respectively. For quantitative analysis ions m/z 64 for d5-EC and m/z 62 for EC were applied.
Quality assurance and quality control (QA/QC) Working standard solutions were prepared from stock solutions and step by step diluted with blank matrix to prepare a sequence with concentrations of 10, 20, 50, 100 and 200 µg l−1 while IS was 100 µg l−1. A high correlation coefficient (r2 > 0.999) was obtained for the tested interval. Blank samples were performed every 10 samples. Spiking experiments of EC (n = 3) done in wine sauce at 8, 50 and 200 μg kg−1, gave recoveries of 70.7–78.9%, 87.8–93.4% and 94.5–108%, respectively (Table 1). The limit of detection (LOD) was calculated as three times the procedural blank. LOD of EC was 4 μg kg−1 and the limit of quantification (LOQ) was 10 μg kg−1 (Liu et al. 2011). Method reproducibility studies were done by injecting three replicates of the same standard solution on three different days and on the same day. Both intra- and inter-day precision showed relative standard deviations of below 15%, indicating good method performance. Results and discussion Analysis of EC in wines, grain spirits and wine sauce during 2009–2012 was completed and the results are given in the database. Figure 1 visualises the relatively constant trend over the years. Until now only Canada has maintained maximum levels for the presence of EC in a variety of alcoholic beverages. These limits vary from 30 μg l–1 for wine to 400 μg l–1 for fruit brandies (Health Canada 2012). Since wine was
believed to usually exceed this limit (30 μg l−1), wine samples were studied in greater detail (n = 212). About 19% of the wines under study exceeded 30 μg l−1. In nearly all wine samples, EC was detected with the exception of two 2009 samples (n = 40), two 2010 samples (n = 57) and one 2011 sample (n = 55). The average EC concentrations of the wine samples were 21.0, 14.8, 20.6 and 22.1 μg kg−1 in 2009–2012, respectively. In the wines of year 2012 (n = 60), the highest level of EC was obtained (87.8 μg kg−1). Furthermore, it is estimated that nearly 80% of EC found in grain spirits is formed during the distillation step and/or within the first 48 h after the distillation (Aresta et al. 2001; Bruno et al. 2007; Fox & Stachowiak 2007). Thus, different adapted strategies could be successfully developed and used in industrial scale to lower the EC level. EC content in nearly all grain spirits (n = 143) was below the Canadian limit of 150 μg l−1, except one 2011 sample which contained 189 μg kg−1. However, 100% incidence of EC in grain spirits under study was found and higher levels of EC were also detected in a minority of distilled spirits (above 100 μg kg−1). In the spirits of the years 2009–2012, the mean values of EC were 40.1, 33.8 and 42.7 μg kg−1, respectively. Most of the wine sauce samples (n = 164) contained either no EC (n = 55), or traces, with the exception of three 2009 wines, four 2010 wines, four 2011 wines and one 2012 wine, which have higher than 30 μg l−1. Additionally, the average EC content in wine sauce samples remained very constant over the 4 years, being 8.2, 8.7, 7.8 and 8.6 μg kg−1, respectively. Contamination of EC in wines (2–87.8 μg kg−1) and in grain spirits (2.9–189 μg kg−1) in this study was a little higher than those published elsewhere (Uthurry et al. 2004; Hasnip et al. 2007; Hong et al. 2007). It shows attention must be paid to monitor and control EC in alcoholic beverages and other fermented foods in order to protect the consumer health.
216
Y. Liu et al. (a)
(b)
100
200
–1 Content (µg kg )
–1
Content (µg kg )
80 60 40
150
100
20
0
0 2009
2010
Year
(c)
2011
2009
2012
2010 Year
2012
70 60 50
–1 Content (µg kg )
Downloaded by [University of Windsor] at 16:55 12 November 2014
50
40 30 20 10 0 –10 2009
2010
Year
2011
2012
Figure 1. Box-plots for ethyl carbamate concentrations in alcoholic beverages in 2009–2012 (no data for grain spirits in 2012). Concentrations of EC in (a) wines; (b) grain spirits and (c) wine sauce are displayed (n = 40–60). Median value (horizontal centre line), 25%- and 75%-quartiles (box) and minimum and maximum values (vertical line) are shown.
Conclusions Contamination of EC in a variety of alcoholic beverages in successive 4 years (2009–2012) was relatively constant. Further studies are recommended to investigate EC levels in other areas of China. Evaluation of the results combined with Chinese consumption patterns and ADI (acceptable daily intake) values could lead to the development of limits for EC in Chinese fermented wines and spirits.
References Aresta M, Boscolo M, Franco DW. 2001. Copper (II) catalysis in cyanate conversion into ethyl carbamate in spirits, and relevant reactions. J Agric Food Chem. 49:2819–2824. Battaglia R, Conacher BS, Page BD. 1990. Ethyl carbamate in alcoholic beverages and foods: a review. Food Addit Contam. 7:477–496. Beland FA, Benson WR, Mellick PW, Kovatch RM, Roberts DW, Fang JL, Doerge DR. 2005. Effect of ethanol on the tumoriginity of urethane (ethyl carbamate) in B6C3F1 mice. Food Chem Technol. 43:1–19. Bruno SNF, Vaitsman DS, Kunigami CN, Brasil MG. 2007. Influence of the distillation processes from Rio de Janeiro
in the ethyl carbamate formation in Brazilian sugar cane spirits. Food Chem. 104:1345–1352. Food and Agriculture Organisation of the United Nations/World Health Organisation. 2006. Safety evaluation of certain contaminants in food. Prepared by the Sixty-fourth meeting of the Joint FAO/WHO Expert Committee on Food Additives (JECFA). FAO Food Nutr. Pap. 82:1–778. Fox NJ, Stachowiak GW. 2007. Vegetable oil-based lubricants – a review of oxidation. Tribol Int. 40:1035–1046. Hasnip S, Crew C, Potter N, Christy J, Chan D, Bondu T, Matthews W, Walters B, Patel K. 2007. Survey of ethyl carbamate in fermented foods sold in the United Kingdom in 2004. J Agric Food Chem. 55:2755–2759. Health Canada. 2012. Health Canada, Ottawa, Ontario, Food and Drugs Act 1985. [Internet]. [cited 2012 Oct 25]. Available from: http://www.hc-sc.gc.ca/fn-an/securit/chem-chim/ contaminants-guidelines-directives-eng.php Hong KP, Kang YS, Jung DC, Park SR, Yoon JH, Lee SY, Ko YS, Kim SH, Ha SD, Park SK, et al. 2007. Exposure to ethyl carbamate by consumption of alcoholic beverages imported in Korea. Food Sci Biotechnol. 16:975–980. International Agency for Research on Cancer. 2007. International Agency for Research. Volume 96: Alcoholic Beverage Consumption and Ethyl Carbamate (Urethane) 2007 Feb 6–13; Lyon: World Health Organization; p. 1–5
Food Additives & Contaminants: Part B
Downloaded by [University of Windsor] at 16:55 12 November 2014
Lachenmeier DW, Kanteres F, Kuballa T, López MG, Rehm J. 2009. Ethyl carbamate in alcoholic beverages from Mexico (Tequila, Mezcal, Bacanora, Sotol) and Guatemala (Cuxa): market survey and risk assessment. Int J Environ Res Public Health. 6:349–360. Lachenmeier DW, Schehl B, Kuballa T, Frank W, Senn T. 2005. Retrospective trends and current status of ethyl carbamate in German stone-fruit spirits. Food Addit Contam. 22:397–405. Liu YP, Dong B, Qin ZS, Yang NJ, Lu Y, Yang LX, Chang FQ, Wu YN. 2011. Ethyl carbamate levels in wine and spirits from markets in Hebei Province, China. Food Addit Contam Part B. 4:1–5.
217
Park SR, Ha SD, Yoon JH, Lee SY, Hong KP, Lee EH, Yeom HJ, Yoon NG, Bae DH. 2009. Exposure to ethyl carbamate in alcohol-drinking and nondrinking adults and its reduction by simple charcoal filtration. Food Contr. 20:946–952. Susana MA, Arminda A, Beatriz O, Paulo H. 2005. Determination of ethyl carbamate in alcoholic beverages: an interlaboratory study to compare HPLC-FLD with GC-MS methods. Anal Bioanal Chem. 382:498–503. Uthurry CA, Varela F, Colomo B, Suárez Lepe JA, Lombardero J, García del Hierro JR. 2004. Ethyl carbamate concentrations of typical Spanish red wines. Food Chem. 88:329–336.
Food Additives & Contaminants: Part B: Surveillance Publication details, including instructions for authors and subscription information: http://www.tandfonline.com/loi/tfab20
A survey of levels of ethyl carbamate in alcoholic beverages in 2009–2012, Hebei Province, China a
b
Yinping Liu , Shuhui Wang & Ping Hu
b
a
Hebei Provincial Center for Disease Control and Prevention , Shijiazhuang , 050021 , People's Republic of China b
Shijiazhuang Center for Disease Control and Prevention , Shijiazhuang , 050019 , People's Republic of China Accepted author version posted online: 10 May 2013.Published online: 21 Jun 2013.
To cite this article: Yinping Liu , Shuhui Wang & Ping Hu (2013) A survey of levels of ethyl carbamate in alcoholic beverages in 2009–2012, Hebei Province, China, Food Additives & Contaminants: Part B: Surveillance, 6:3, 214-217, DOI: 10.1080/19393210.2013.803162 To link to this article: http://dx.doi.org/10.1080/19393210.2013.803162
PLEASE SCROLL DOWN FOR ARTICLE Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and should be independently verified with primary sources of information. Taylor and Francis shall not be liable for any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of the Content. This article may be used for research, teaching, and private study purposes. Any substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http:// www.tandfonline.com/page/terms-and-conditions
Food Additives & Contaminants: Part B, 2013 Vol. 6, No. 3, 214–217, http://dx.doi.org/10.1080/19393210.2013.803162
A survey of levels of ethyl carbamate in alcoholic beverages in 2009–2012, Hebei Province, China Yinping Liua, Shuhui Wangb and Ping Hub* a Hebei Provincial Center for Disease Control and Prevention, Shijiazhuang 050021, People’s Republic of China; bShijiazhuang Center for Disease Control and Prevention, Shijiazhuang 050019, People’s Republic of China
Downloaded by [University of Windsor] at 16:55 12 November 2014
(Received 22 December 2012; final version received 3 May 2013) Results of a survey of levels of ethyl carbamate (EC) (urethane) in alcoholic beverages carried out in four successive years from 2009 to 2012 by gas chromatography-mass spectrometry (GC/MS) are presented. The beverages were purchased for sampling from Hebei Province of China, including eight main areas of production. The samples comprised wines (n = 212), grain spirits (n = 143) and wine sauces (n = 164). The data show that the average EC content in these kinds of alcoholic beverages remains nearly constant over the years. The results provide valuable data for food authorities to establish maximum limits for EC in China. Keywords: ethyl carbamate; alcoholic beverages; GC/MS; variation tendency
Introduction Ethyl carbamate (EC) is ethyl ester of carbamic acid and has widespread occurrence in fermented foods and beverages, with levels ranging from nanograms per litre to milligrams per litre (Battaglia et al. 1990; Uthurry et al. 2004; Lachenmeier et al. 2005, 2009; Susana et al. 2005; Park et al. 2009). EC is genotoxic and carcinogenic, and thus a potential carcinogenic risk to humans (Beland et al. 2005). It has been classified as a group 2A carcinogen, i.e. “probably carcinogenic to humans,” by the World Health Organization’s International Agency for Research on Cancer (2007). Since alcoholic drinks are considered as a source of ethyl carbamate, the issue of EC in alcoholic beverages has attracted a great deal of attention in many countries. JECFA (Joint FAO/WHO Expert Committee on Food Additives) estimated a dietary exposure of 17 ng/kg b.w. per day (Food and Agriculture Organisation of the United Nations/World Health Organisation 2006). Main alcoholic beverages consumed in Hebei are wines, grain spirits and wine sauces, so this surveillance focused on EC in these alcoholic beverages from 2009 to 2012. It aimed to search for variation tendency and to provide data for authorities for risk assessment and evaluate establishment of maximum limits for EC in China.
Materials and methods Samples Samples were collected at local markets from eight areas (Shijiazhuang, Baoding, Handan, Qinhuangdao, Langfang, Zhangjiakou, Xingtai and Cangzhou) in the *Corresponding author. Email: [email protected] © 2013 Taylor & Francis
Hebei Province, China. All were domestic alcoholic beverages. The total number of investigated samples consisted of 212 wines and 164 wine sauces (years 2009–2012) and 143 grain spirits (years 2009–2011). No grain spirits were sampled in 2012. Chemicals All solvents were high-pressure liquid chromatography (HPLC)-grade and purchased from J.T. Baker (Philipsburg, CA, USA). The CLE diatomaceous earth columns were provide by Hangzhou Fuyu Technology Service Company Limited (Hangzhou, China). The EC standard (99%) was from Sigma-Aldrich (Madrid, Spain) and the d5-EC internal standard (IS, 99%) was from Cambridge Isotope Laboratory (Andover, MA, USA). Chemical analysis Sample analysis was performed following the procedure described in a previous study (Liu et al. 2011). Briefly, 2.0-g sample was grounded with a known amount of IS, and then subjected to a CLE column. After an equilibration time of 15 min, the analytes were extracted using 10 ml of ethyl ether. The eluate was reduced to dryness under gentle nitrogen gas and re-dissolved in methanol to 1 ml before injection into the gas chromatography-mass spectrometry (GC-MS). A Thermo Trace-GC with an ultra-DSQ mass spectrometer (Thermo Fisher Scientific Inc., Waltham, MA, USA) equipped with A HP-Innowax capillary column (30 m × 0.25 mm × 0.25 µm, Agilent Technologies, Santa Clara, CA, USA) was used for the separation and determination of EC in the extracts.
Food Additives & Contaminants: Part B
215
Table 1. Recoveries and relative standard deviations (RSDs) for EC in wine sauce. Determined times
Spiking level (µg kg−1)
Determined result (µg kg−1)
Recovery (%)
Average recovery (%)
RSDs (%)
8 8 8 50 50 50 200 200 200
6.0 6.3 5.7 46.7 45.6 43.9 189 191 216
75.1 78.9 70.7 93.4 91.2 87.8 94.5 95.5 108.0
74.9
5.4
90.8
3.1
99.3
7.6
Downloaded by [University of Windsor] at 16:55 12 November 2014
1 2 3 1 2 3 1 2 3
Column temperature was held at 60°C for 3 min., then programmed at a rate of 8°C min−1 to 160°C, with a postrun temperature of 240°C for 5 min. Ion source and transfer line temperatures were 230°C and 250°C, respectively. For quantitative analysis ions m/z 64 for d5-EC and m/z 62 for EC were applied.
Quality assurance and quality control (QA/QC) Working standard solutions were prepared from stock solutions and step by step diluted with blank matrix to prepare a sequence with concentrations of 10, 20, 50, 100 and 200 µg l−1 while IS was 100 µg l−1. A high correlation coefficient (r2 > 0.999) was obtained for the tested interval. Blank samples were performed every 10 samples. Spiking experiments of EC (n = 3) done in wine sauce at 8, 50 and 200 μg kg−1, gave recoveries of 70.7–78.9%, 87.8–93.4% and 94.5–108%, respectively (Table 1). The limit of detection (LOD) was calculated as three times the procedural blank. LOD of EC was 4 μg kg−1 and the limit of quantification (LOQ) was 10 μg kg−1 (Liu et al. 2011). Method reproducibility studies were done by injecting three replicates of the same standard solution on three different days and on the same day. Both intra- and inter-day precision showed relative standard deviations of below 15%, indicating good method performance. Results and discussion Analysis of EC in wines, grain spirits and wine sauce during 2009–2012 was completed and the results are given in the database. Figure 1 visualises the relatively constant trend over the years. Until now only Canada has maintained maximum levels for the presence of EC in a variety of alcoholic beverages. These limits vary from 30 μg l–1 for wine to 400 μg l–1 for fruit brandies (Health Canada 2012). Since wine was
believed to usually exceed this limit (30 μg l−1), wine samples were studied in greater detail (n = 212). About 19% of the wines under study exceeded 30 μg l−1. In nearly all wine samples, EC was detected with the exception of two 2009 samples (n = 40), two 2010 samples (n = 57) and one 2011 sample (n = 55). The average EC concentrations of the wine samples were 21.0, 14.8, 20.6 and 22.1 μg kg−1 in 2009–2012, respectively. In the wines of year 2012 (n = 60), the highest level of EC was obtained (87.8 μg kg−1). Furthermore, it is estimated that nearly 80% of EC found in grain spirits is formed during the distillation step and/or within the first 48 h after the distillation (Aresta et al. 2001; Bruno et al. 2007; Fox & Stachowiak 2007). Thus, different adapted strategies could be successfully developed and used in industrial scale to lower the EC level. EC content in nearly all grain spirits (n = 143) was below the Canadian limit of 150 μg l−1, except one 2011 sample which contained 189 μg kg−1. However, 100% incidence of EC in grain spirits under study was found and higher levels of EC were also detected in a minority of distilled spirits (above 100 μg kg−1). In the spirits of the years 2009–2012, the mean values of EC were 40.1, 33.8 and 42.7 μg kg−1, respectively. Most of the wine sauce samples (n = 164) contained either no EC (n = 55), or traces, with the exception of three 2009 wines, four 2010 wines, four 2011 wines and one 2012 wine, which have higher than 30 μg l−1. Additionally, the average EC content in wine sauce samples remained very constant over the 4 years, being 8.2, 8.7, 7.8 and 8.6 μg kg−1, respectively. Contamination of EC in wines (2–87.8 μg kg−1) and in grain spirits (2.9–189 μg kg−1) in this study was a little higher than those published elsewhere (Uthurry et al. 2004; Hasnip et al. 2007; Hong et al. 2007). It shows attention must be paid to monitor and control EC in alcoholic beverages and other fermented foods in order to protect the consumer health.
216
Y. Liu et al. (a)
(b)
100
200
–1 Content (µg kg )
–1
Content (µg kg )
80 60 40
150
100
20
0
0 2009
2010
Year
(c)
2011
2009
2012
2010 Year
2012
70 60 50
–1 Content (µg kg )
Downloaded by [University of Windsor] at 16:55 12 November 2014
50
40 30 20 10 0 –10 2009
2010
Year
2011
2012
Figure 1. Box-plots for ethyl carbamate concentrations in alcoholic beverages in 2009–2012 (no data for grain spirits in 2012). Concentrations of EC in (a) wines; (b) grain spirits and (c) wine sauce are displayed (n = 40–60). Median value (horizontal centre line), 25%- and 75%-quartiles (box) and minimum and maximum values (vertical line) are shown.
Conclusions Contamination of EC in a variety of alcoholic beverages in successive 4 years (2009–2012) was relatively constant. Further studies are recommended to investigate EC levels in other areas of China. Evaluation of the results combined with Chinese consumption patterns and ADI (acceptable daily intake) values could lead to the development of limits for EC in Chinese fermented wines and spirits.
References Aresta M, Boscolo M, Franco DW. 2001. Copper (II) catalysis in cyanate conversion into ethyl carbamate in spirits, and relevant reactions. J Agric Food Chem. 49:2819–2824. Battaglia R, Conacher BS, Page BD. 1990. Ethyl carbamate in alcoholic beverages and foods: a review. Food Addit Contam. 7:477–496. Beland FA, Benson WR, Mellick PW, Kovatch RM, Roberts DW, Fang JL, Doerge DR. 2005. Effect of ethanol on the tumoriginity of urethane (ethyl carbamate) in B6C3F1 mice. Food Chem Technol. 43:1–19. Bruno SNF, Vaitsman DS, Kunigami CN, Brasil MG. 2007. Influence of the distillation processes from Rio de Janeiro
in the ethyl carbamate formation in Brazilian sugar cane spirits. Food Chem. 104:1345–1352. Food and Agriculture Organisation of the United Nations/World Health Organisation. 2006. Safety evaluation of certain contaminants in food. Prepared by the Sixty-fourth meeting of the Joint FAO/WHO Expert Committee on Food Additives (JECFA). FAO Food Nutr. Pap. 82:1–778. Fox NJ, Stachowiak GW. 2007. Vegetable oil-based lubricants – a review of oxidation. Tribol Int. 40:1035–1046. Hasnip S, Crew C, Potter N, Christy J, Chan D, Bondu T, Matthews W, Walters B, Patel K. 2007. Survey of ethyl carbamate in fermented foods sold in the United Kingdom in 2004. J Agric Food Chem. 55:2755–2759. Health Canada. 2012. Health Canada, Ottawa, Ontario, Food and Drugs Act 1985. [Internet]. [cited 2012 Oct 25]. Available from: http://www.hc-sc.gc.ca/fn-an/securit/chem-chim/ contaminants-guidelines-directives-eng.php Hong KP, Kang YS, Jung DC, Park SR, Yoon JH, Lee SY, Ko YS, Kim SH, Ha SD, Park SK, et al. 2007. Exposure to ethyl carbamate by consumption of alcoholic beverages imported in Korea. Food Sci Biotechnol. 16:975–980. International Agency for Research on Cancer. 2007. International Agency for Research. Volume 96: Alcoholic Beverage Consumption and Ethyl Carbamate (Urethane) 2007 Feb 6–13; Lyon: World Health Organization; p. 1–5
Food Additives & Contaminants: Part B
Downloaded by [University of Windsor] at 16:55 12 November 2014
Lachenmeier DW, Kanteres F, Kuballa T, López MG, Rehm J. 2009. Ethyl carbamate in alcoholic beverages from Mexico (Tequila, Mezcal, Bacanora, Sotol) and Guatemala (Cuxa): market survey and risk assessment. Int J Environ Res Public Health. 6:349–360. Lachenmeier DW, Schehl B, Kuballa T, Frank W, Senn T. 2005. Retrospective trends and current status of ethyl carbamate in German stone-fruit spirits. Food Addit Contam. 22:397–405. Liu YP, Dong B, Qin ZS, Yang NJ, Lu Y, Yang LX, Chang FQ, Wu YN. 2011. Ethyl carbamate levels in wine and spirits from markets in Hebei Province, China. Food Addit Contam Part B. 4:1–5.
217
Park SR, Ha SD, Yoon JH, Lee SY, Hong KP, Lee EH, Yeom HJ, Yoon NG, Bae DH. 2009. Exposure to ethyl carbamate in alcohol-drinking and nondrinking adults and its reduction by simple charcoal filtration. Food Contr. 20:946–952. Susana MA, Arminda A, Beatriz O, Paulo H. 2005. Determination of ethyl carbamate in alcoholic beverages: an interlaboratory study to compare HPLC-FLD with GC-MS methods. Anal Bioanal Chem. 382:498–503. Uthurry CA, Varela F, Colomo B, Suárez Lepe JA, Lombardero J, García del Hierro JR. 2004. Ethyl carbamate concentrations of typical Spanish red wines. Food Chem. 88:329–336.
