Coumarin content in cinnamon containing food products on the Danish market
Introduction
The cinnamon used domestically and industrially in the preparation of food originates primarily from true cinnamon and from cassia cinnamon (simply referred to as cassia). True cinnamon belongs to the species of Cinnamomum verum J. S. Presl whereas cassia generally include the species of Cinnamomum cassia J. Presl, also known as Cinnamomum aromaticus Nees, Cinnamomum loureiroi Nees and Cinnamomum burmannii Blume (Ravindran et al., 2004, WHO, 1999). Cassia is cheaper and generally more popular in Europe compared to true cinnamon (Blahova and Svobodova, 2012, Lungarini et al., 2008). True cinnamon and cassia taste different because of a different chemical composition. For example, cassia contains more of the aromatic compound coumarin (1-benzopyran-2-one) compared to true cinnamon (Miller et al., 1996, Sproll et al., 2008). Coumarin was regarded as a possible genotoxic carcinogen in the 1980th and 1990th and the European Union set a general coumarin limit in food to 2 mg/kg (European Council, 1988, Lake, 1999). In 2004, new scientific data on coumarin showed a non-genotoxic carcinogenic effect, but it also showed that a subgroup of individuals was sensitive to a hepatotoxic effect from coumarin (Abraham, Wöhrlin, Lindtner, Heinemeyer, & Lampen, 2010). These data allowed the European Food Safety Authority (EFSA) to derive a tolerable daily intake (TDI) of 0–0.1 mg coumarin/kg body weight (EFSA, 2004). In 2005, a high content of coumarin in cookies (BfR, 2006) initiated increased authoritarian coumarin control and debate (Abraham et al., 2010, VKM, 2010). This, in combination with a widespread and increased use of cassia in food products, led the European Parliament and Council to evaluate the maximum coumarin limits (European Council, 1988). In 2008, the European Regulation (EC) No 1334/2008 (European Parliament and Council, 2008) was enacted with the following maximum limits for coumarin: 50 mg/kg in traditional and/or seasonal bakery ware containing a reference to cinnamon in the labeling, 20 mg/kg in breakfast cereals including muesli, 15 mg/kg in fine bakery ware, with the exception of traditional and/or seasonal bakery ware containing a reference to cinnamon in the labeling, and 5 mg/kg in desserts. Coumarin should not be added as such to food products.
The content of coumarin varies considerable in cinnamon sticks and in ground cinnamon. The contents of coumarin in cinnamon sticks were reported to be as high as 12,180 mg/kg (He et al., 2005) and 9900 mg/kg (Woehrlin, Fry, Abraham, & Preiss-Weigert, 2010), whereas the content in ground cinnamon was reported to range between 1740 and 7670 mg/kg (Woehrlin et al., 2010), 2650–7017 mg/kg (Blahova & Svobodova, 2012), and 5–3094 mg/kg (Lungarini et al., 2008). This shows that the distribution of coumarin in ground cinnamon is less heterogeneous than in cinnamon sticks. The very low contents (<100 mg/kg) of coumarin observed in cinnamon sticks and in ground cinnamon might originate from Cinnamomum verum samples and not cassia (Lungarini et al., 2008). The high variation of the coumarin content in cinnamon complicates an addition of cinnamon to food products that complies with the EU limits for coumarin.
The content of coumarin in food products was investigated in Germany in 2006–2007 (Sproll et al., 2008) and compared to the former EU limits described in the Council Directive 88/388/EEC (European Council, 1988). These limits for coumarin were 2 mg/kg with the exception of special caramels and alcoholic beverages with a limit of 10 mg/kg, and chewing gum with a limit of 50 mg/kg (European Council, 1988). The investigation showed that 85% of all cinnamon flavored cookies exceeded the EU limit of 2 mg/kg (Sproll et al., 2008). Another study found 100% of cinnamon cookies (n = 10) touching or exceeding the 2 mg/kg limit (Lungarini et al., 2008). In 2012, an inspection program was initiated at the Danish Veterinary and Food Administration (DVFA) to investigate if food products on the Danish market complied with the higher and current EU regulation (European Parliament and Council, 2008). Despite its absence in the EU regulation, we included tea and crisp bread with cinnamon in the investigation to examine its contribution to the coumarin intake.
Quantification of coumarin is primarily performed with chromatographic techniques such as high performance liquid chromatography (HPLC) (He et al., 2005, Lungarini et al., 2008, Maggi, Barboni et al., 2011, Martino et al., 2006, Sproll et al., 2008, Woehrlin et al., 2010), gas chromatography (GC) (Maggi, Martonfi et al., 2011, Miller et al., 1996, Miller et al., 1995, Ochiai et al., 2012), and the more recent introduction of ultra performance liquid chromatography (UPLC) (Wang, Avula, Nanayakkara, Zhao, & Khan, 2013). UPLC has shown its advantage over traditional HPLC and GC analysis with respect to the chromatographic separation time. This paper describes an UPLC method and investigates the coumarin content in Danish food products with cinnamon in relation to the EU limits.
As an addendum, we present a practical guide for Food Administrations and food manufacturers. The practical guide describes the theoretical amount of cassia that can be added to different food products without exceeding the EU limits for coumarin (European Parliament and Council, 2008).
Section snippets
Chemicals and standards
Methanol (99%) and acetonitrile (HPLC grade) were purchased from Fisher Scientific (United Kingdom). Coumarin (≥99%) and 4-methylumbelliferone (≥98%) (MUM) were purchased from Sigma Aldrich (Denmark).
UPLC instrumentation and chromatographic conditions
The Waters Acquity UPLC H-class (Milford, MA) consisted of a separation module and a PDA detector. The system was equipped with a Waters ACQUITY UPLC HSS T3 Column 2.1 × 100 mm, 1.8 μm. The chromatographic system consisted of eluent A and B. Eluent A contained 5% methanol in demineralized water.
Food samples
Coumarin was identified at a retention time around 1.58 min. The RT ratio between MUM and coumarin (Fig. 1) was evaluated and varied with no more than 0.03 from any dilution to any sample. In addition, also the UV profiles (Fig. 2) were compared. In all samples, the UV profile of coumarin was consistent with literature data (Maggi, Barboni, et al., 2011) showing a global maximum at 278.1 nm and a local maximum at around 311 nm (the local maximum was present in all samples but a value was not
Advisory amounts of cassia in food products
Small bakery stores could have difficulties in keeping up with the relevant EU regulations, and might therefore be unaware of the EU limits for coumarin (European Parliament and Council, 2008). However, even knowledge about the EU limits might not answer the question on how much cinnamon that can be added to bakery ware without exceeding the EU limits for coumarin (European Parliament and Council, 2008). We, therefore, find it appropriate to provide food manufacturers with advisory amounts of
Conclusion
The present UPLC method is fast and suitable for routine testing of coumarin in food products with cinnamon. In this study, the presence of cinnamon in fine bakery ware has resulted in several cases of a coumarin content exceeding the EU limit (European Parliament and Council, 2008). The reason for the high incidence of samples exceeding the EU limit for coumarin in bakery ware is unknown. However, a lack of knowledge about the EU regulation (European Parliament and Council, 2008) could be one
Acknowledgment
We thank Kirsten Halkjær Lund and Birgit Christine Bønsager for critical comments on the manuscript.
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2022, Journal of Supercritical FluidsCitation Excerpt :For this reason, coumarins are of high interest for the pharmaceutical industry. Beyond the application as medical drug, due to its vanilla-like odor [21], it is used in cosmetic [22], cleaning detergents [23], and as food additive [24–26]. Although in the European Union the tolerable daily intake is lower than 0.1 mg coumarin / kg body weight /day [27], in the United States of America coumarin consumption is totally prohibited due to its toxicity [28].