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Analysis of furan and its major furan derivatives in coffee products on the
Chinese market using HS-GC-MS and the estimated exposure of the Chinese
population

Article in Food Chemistry · March 2022


DOI: 10.1016/j.foodchem.2022.132823

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Food Chemistry 387 (2022) 132823

Contents lists available at ScienceDirect

Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Analysis of furan and its major furan derivatives in coffee products on the
Chinese market using HS-GC–MS and the estimated exposure of the
Chinese population
Pei Cao a, Lei Zhang a, Yang Yang b, Xiao-dan Wang a, Zhao-ping Liu a, Jian-wen Li a,
Li-yuan Wang c, Sookja Chung d, Moqin Zhou e, Ke Deng e, Ping-ping Zhou a, *, Ping-gu Wu c, *
a
China National Center for Food Safety Risk Assessment, Beijing 100022, China
b
Chinese Academy of Inspection and Quarantine, Beijing 100176, China
c
Zhe Jiang Provincial Center for Disease Control and Prevention, Hangzhou 310051, China
d
Faculty of Medicine, Macau University of Science and Technology, Macao, China
e
Center for Statistical Science & Department of Industrial Engineering, Tsinghua University, Beijing 100084, China

A R T I C L E I N F O A B S T R A C T

Keywords: The current study analysed concentrations of furan and its derivatives in coffee products commercially available
Furan in China based on an improved headspace gas chromatography-mass spectrometry (HS-GC–MS) method and
Furan derivatives estimated health risks. A total of 101 samples of coffee products on the Chinese market was analysed. Furan
Coffee
(98%, ND-6569 μg/kg) and 2-methylfuran (100%, 2–29639 μg/kg) were the compounds with the highest con­
Exposure
HS-GC–MS method
centrations and detection rates in coffee products. The mean dietary exposure of Chinese consumers to furan and
the sum of furan, 2-methylfuran and 3-methylfuran in coffee products was 0.09 and 0.46 μg/kg bw/day,
Chemical compounds studied in this article:
Furan (PubChem CID: 8029)
respectively. For the neoplastic effects of furan, the margin of exposure (MOE) was 14,556 for the mean dietary
2-methylfuran (PubChem CID: 10797) exposure of consumers. For the non-neoplastic effects of furan, MOEs were 711 and 139 for furan and the sum of
3-methylfuran (PubChem CID: 13587) furan, 2-methylfuran and 3-methylfuran, respectively. Overall, a health concern is indicated for coffee consumers
2,5-dimethylfuran (PubChem CID: 12266) with MOEs below 10000.
2-ethylfuran (PubChem CID: 18554)
2-pentylfuran (PubChem CID: 19602)
Furan-d4 (PubChem CID: 2733420)
2-methylfuran-d6 (PubChem CID: 131708589)
3-methylfuran-d3 (PubChem CID: 45039817)
2,5-dimethylfuran-d3 (PubChem CID:
13595812)

1. Introduction (Becalski & Seaman, 2005; Märk, Pollien, Lindinger, Blank, & Märk,
2006; Limacher, Kerler, Conde-Petit, & Blank, 2007). The existence of
Furan (C4H4O) is an oxygenated heterocycle with a series of homo­ furan in foods is a safety concern because it has been identified as an
logues that forms during the thermal treatment of a variety of foods, animal carcinogen and classified as a possible human carcinogen (Group
including coffee, canned and jarred food, cereals, and baked bread 2B) by the International Agency for Research on Cancer (IARC) (IARC,
(Moro, Chipman, Wegener, Hamberger, Dekant, & Mally, 2012; Rahn & 1995; NTP, 2004). In addition to furan, methylfurans (such as 2-methyl­
Yeretzian, 2019). The generation of furan is mainly caused by the furan, 3-methylfuran and 2,5-dimethylfuran) and other alkylfurans (2-
thermal degradation of carbohydrates, the oxidation of polyunsaturated ethylfuran and 2-pentylfuran) can be formed and co-occur during
fatty acids and the decomposition of ascorbic acid or its derivatives thermal processing (EFSA, 2017; Frank, Dubois, & Huertas Pérez, 2020).

* Corresponding authors.
E-mail addresses: caopei@cfsa.net.cn (P. Cao), Zhanglei@cfsa.net.cn (L. Zhang), yang031061yang@163.com (Y. Yang), wangxiaodan@cfsa.net.cn (X.-d. Wang),
lijianwen@cfsa.net.cn (J.-w. Li), lywang@cdc.zj.cn (L.-y. Wang), skchung@must.edu.mo (S. Chung), kdeng@tsinghua.edu.cn (K. Deng), zhoupingping@cfsa.net.cn
(P.-p. Zhou), pgwu@cdc.zj.cn (P.-g. Wu).

https://doi.org/10.1016/j.foodchem.2022.132823
Received 23 February 2021; Received in revised form 24 March 2022; Accepted 24 March 2022
Available online 26 March 2022
0308-8146/© 2022 Elsevier Ltd. All rights reserved.
P. Cao et al. Food Chemistry 387 (2022) 132823

However, current toxicology studies on furan derivatives are still not purchased from Chem Service Inc. (Pennsylvania, United States). The
sufficient. d4-furan internal standard acetonitrile solution (100 μg/mL, > 99%) was
Coffee contains higher levels of furan and its derivatives than other purchased from Dr. Ehrenstorfer GmbH (Augsburg, Germany), and d6-2-
processed foods, with the residues ranging from maximum parts-per- methylfuran (>99%), d3-3-methylfuran (>99%), d5-2-ethylfuran
billion (ppb) levels to tens of parts-per-million (ppm) (Altaki, Santos, (>99%), d3-2,5-dimethylfuran (>99%) and d11-2-pentylfuran (>99%)
Galceran, 2011; EFSA, 2011; Becalski, Halldorson, Hayward, & Roscoe, were purchased from Toronto Research Chemicals (Toronto, Canada).
2016; Rahn & Yeretzian, 2019). Currently, the methods used for All these standards were stored at − 20 ◦ C and kept away from light.
measuring furan and furan derivatives in foods include headspace (HS) Methanol (>99%, HPLC-grade) and sodium chloride were obtained from
or headspace solid-phase microextraction (HS-SPME), which both are Merck (Darmstadt, Germany) and Sinopharm (Beijing, China). In addi­
coupled to gas chromatography-mass spectrometry (GC–MS). However, tion, sodium chloride was baked in an oven (200 ◦ C) for 2 h (hrs) and
SPME is not suitable for foods containing high levels of furan, such as cooled to room temperature, and dissolved in water (analytical grade).
coffee (Arisseto, Vicente, Ueno, Tfouni, & Toledo, 2011; Condurso,
Cincotta, & Verzera, 2018; Frank, Dubois, & Huertas Pérez, 2020). 2.2. Standard solution preparation
Furthermore, most of these studies focused on furan and methylfuran,
but few involved alkylfurans. Previously, the concentrations of furan, 2- The mixed stock standard solution (2.0 mg/mL) with 2-methylfuran,
methylfuran, 3-methylfuran, 2,5-dimethylfuran and 2,3-dimethylfuran 3-methylfuran, 2-ethylfuran, 2-pentylfuran and 2,5-dimethylfuran was
in different coffee products were analysed by HS-GC–MS. prepared by adding 50 mg of each compound into a 25-mL volumetric
and determined the influence of consumer behaviour on the levels of flask with methanol. Mixed working standard solutions were prepared
furan and its derivatives (Rahn & Yeretzian, 2019). In addition, furan, 2- by serial dilution of the mixed standard intermediate solutions using
methylfuran, 3-methylfuran, 2,5-dimethylfuran, 2-ethylfuran and 2- methanol at concentrations of 0.1 μg/mL or 1.0 μg/mL.
pentylfuran were analysed in coffee samples (roasted and ground cof­ A mixed stock internal standard solution (10.0 μg/mL) was prepared
fee and soluble coffee) using HS-GC–MS based on an HP-PLOT Q column by dissolving 0.2 mL of d6-2-methylfuran, d3-3-methylfuran and d5-2-
(Frank, Dubois, & Huertas Pérez, 2020). However, the use of HP-PLOT Q ethylfuran and 1.0 mL of d3-2,5-dimethylfuran and d11-2-pentylfuran
column had a limitation in quantitative analysis, since it was not able to into a 10-mL volumetric flask in methanol. Another mixed working in­
completely separate 2-ethylfuran and 2,5-dimethyl furan with a reso­ ternal standard solution at 1.0 μg/mL concentration was also prepared
lution of chromatographic peaks of approximately 1 (BS EN by adding 1.0 mL of mixed stock internal standard solution and 5.0 mL
16620:2015; Frank, Dubois, & Huertas Pérez, 2020). of d4-furaninternal standard intermediate solution (2.0 μg/mL) into a
As mentioned above, furan and its derivatives are widely distributed 10-mL volumetric flask with methanol. All the standard solutions were
in processed foods, which are formed in domestic cooking practices. stored at − 20 ◦ C and kept away from light.
Regular consumption of coffee is one of the key dietary behaviour in
Western countries and may play an important role in dietary exposure to 2.3. Optimization of sodium chloride concentration in solution
furan, which has a high content in coffee (Scholl, Humblet, Scippo, De
Pauw, Eppe, & Saegerman, 2012; Becalski, Halldorson, Hayward, & In 2004, the U.S. Food and Drug Administration (US FDA) published
Roscoe, 2016; Mayerhofer, Czerwenka, Marchart, Steinwider, & Hof­ a static HS-GC–MS method to analyse furan with the standard addition
staedter, 2019). In 2017, the European Food Safety Authority (EFSA) approach, which used saturated sodium chloride to dissolve samples to
published a scientific opinion on the risk assessment of furan and avoid the impact of ethanol produced by fermentation (US-FDA, 2004).
methylfurans in food in a European population, revealing that coffee, In this study, we compared the recoveries of six internal standard
especially roasted coffee beans and roasted coffee powder, is the major compounds from coffee samples (coffee powder and instant coffee
contributor to adult furan exposure (EFSA, 2017). Previously, the level powder) dissolved in pure water, 10% sodium chloride solution, 20%
of furan was determined in foods (including traditional Chinese liquor, sodium chloride solution and saturated sodium chloride solution,
coffee, tea, and pickles) in China and estimated the dietary exposure to respectively. It is found that the recoveries of d5-2-ethylfuran, d3-2,5-
furan among the Chinese population. However, this study didn’t esti­ dimethylfuran and d11-2-pentylfuran decreased with increasing sodium
mate the dietary intake of furan through consumption of coffee (Wu, chloride concentration, whereas the recoveries of d4-furan, d6-2-meth­
Wang, & Yuan, 2014). With the growing popularity of coffee in China, it ylfuran and d3-3-methylfuran was not significantly affected by different
has become the widely consumed drink nowadays in Chinese people, concentrations of sodium chloride. It is possible is that the instant coffee
who traditionally enjoy drinking tea. However, limited information has powder contained oil, which facilitates the formation of an isolation
been reported in China regarding the exposure to furan and its de­ layer with the existence of high concentration of sodium chloride. This
rivatives from coffee. may also affect the capability of the furan compounds from the liquid
The aim of this study was to analyse the levels of furan and its five layer volatilize into the gas layer of the headspace vials. Therefore, 20%
major furan derivatives. sodium chloride solution was used to dissolve the coffee samples in the
(2-methylfuran, 3-methylfuran and 2,5-dimethylfuran, 2-ethylfuran current study.
and 2-pentylfuran) in coffee products commercially available in China
with an improved HS-GC–MS method and to assess the health risks of 2.4. Sample collection and preparation
furan exposure in Chinese coffee consumers. In addition, as furan has
possibly carcinogenic and genotoxic effects, the margin of exposure A total of 101 samples of coffee products (including 31 packaged
(MOE) approach was used to estimate exposure to furan, as well as the coffee drinks, 19 roasted ground coffees, 27 roasted beans, 13 instant
combined exposure to furan, 2-methylfuran and 3-methylfuran. coffees and 11 take-out coffees), selected from the most consumed
brands in China, were obtained from the major markets and shopping
2. Materials and methods websites in Beijing and Hangzhou (China). These coffee products
included major domestic and imported brands (including international
2.1. Chemicals and reagents coffee brands from Germany, Italy, Japan, Vietnam, Portugal, Malaysia,
Switzerland, Colombia, and Indonesia), as well as different levels of
Furan standard methanol solution (100 μg/mL, > 99%) was pur­ grinding and roasting. All the samples were collected and stored at −
chased from MANHAGE Bio-Technology Co. Ltd. (Beijing, China), 4 ◦ C in a sealed container and analysed within one month after purchase.
whereas 2-methylfuran (>98%), 3-methylfuran (>98%), 2-ethylfuran The roasted coffee beans (after freezing at − 20 ◦ C for 2 hrs) were
(>98%), 2-pentylfuran (>98%) and 2,5-dimethylfuran(>98%) were ground by a food grinder (Ika Tube Mill CS025) to powder with a size

2
P. Cao et al. Food Chemistry 387 (2022) 132823

less than 60 mesh and were then stored at − 20 ◦ C. A total of 0.2 g of 2.7. Method validation
precooled solid coffee sample or 1.0 g of precooled liquid coffee sample
was added into a 20 mL headspace vial, together with 10 mL of cooled The improved HS-GC–MS method was performed via the routine
sodium chloride solution (20% w/w, 4 ◦ C) and 100 μL mixed working analysis of procedural blanks and quality standards and samples to
internal standard solution (1.0 μL/mL). The vial was capped and crim­ verify the blank samples and to test whether there was possible carry­
ped immediately, and mixed the solution in the vial using a vortex mixer over between samples. The validation of the method depended on the
for 15 s, prior to HS-GC–MS analysis. linearity, limit of detection (LOD), limit of quantitation (LOQ), repeat­
ability, reproducibility and recovery.
The linearity, the coefficient of determination (R2) was calculated
2.5. HS-GC–MS analysis from the responses of 2, 5, 10, 20, 50, 100, 200, 400 ng standard in vials
with an internal standard amount of 100 ng. The data points of cali­
Furan and its five major furan derivatives in coffee samples were bration are shown in Table S2. The LOD and LOQ were estimated as a
analysed using an automated HS method. A mixture of 1 mL (or 1 g) of signal-to-noise (S/N) ratios at 3 and 10, respectively. The LOQs of the
coffee sample, 9 mL of sodium chloride solution (4 ◦ C), and 100 μL improved method were matrix-dependent. For liquid coffee products
mixed working internal standard solution were added to a 20-mL with low concentrations of furan and its derivatives, the LOQs were
headspace vial prior to immediate sealing of the vial. Before analysis, determined as the lowest spiking level (5.0 μg/kg) that corresponds to S/
the sample vial was incubated for 30 min at 60 ◦ C with shaking at 500 N of 10 with acceptable precision and accuracy (Table S3). For solid
rpm. The sample was delivered into a split inlet with a 2:1 split ratio at a coffee products that naturally contain high levels of furan and its de­
flow rate of 30 mL/min and the cycle duration of 35 min. rivatives and when suitable matrix blanks are not available (for all or
An HP-PLOT Q column (15 m, 0.32 mm I.D, 20 µm film) was adopted certain analytes). Spiking experiments were conducted for the affected
to detect furan using the US FDA method. However, this column could analytes at two levels (3 and 10 times of the analyte level in the eval­
not completely separate 2-ethylfuran and 2,5-dimethylfuran with a long uated matrix). In this case, the LOQs were estimated by extrapolating the
running time (Frank, Dubois, & Huertas Pérez, 2020). In our study, DB- S/N ratio obtained for a concentration naturally presented in the eval­
1MS (30 m × 0.25 mm I.D., with a 1.0 μm film thickness), DB-5MS (30 uated matrix to a concentration level that would correspond to S/N = 10
m × 0.25 mm I.D., with a 1.0 μm film thickness), DB-1701MS (30 m × (Table S4). The LODs and LOQs of furan and its derivatives in liquid
0.25 mm I.D., with a 0.25 μm film thickness), DB-Innwax (30 m × 0.25 coffee products were 1.5 and 5.0 μg/kg, respectively, and those in solid
mm I.D., with a 0.25 μm film thickness) and DB-624 (30 m × 0.25 mm I. coffee products were 6.0 and 20.0 μg/kg, respectively.
D., with a 1.4 μm film thickness) were compared. The results showed Precision (including intraday repeatability, RSDr and interday
that DB-624 separated the furan compounds successfully with the 2.3 reproducibility, RSDR) and recovery of the method were evaluated by
degree of separation for 2-ethylfuran and 2,5-dimethylfuran. In addi­ performing spiked experiments with coffee samples. RSDr was calcu­
tion, this method reduced the running time. The total ion flow chro­ lated by spiking the standard solutions to the low background furan
matogram of furan, its derivatives and their internal standards is shown matrices at concentrations of 40 and 400 μg/kg for solid coffee samples
in Fig. S1 of the supplementary document. and 20 and 200 μg/kg for coffee drinks and analysing the run on the
GC analyses were carried out with an Agilent 7890B gas chromato­ same day. The RSDR at two concentrations were calculated via per­
graph (Agilent Technologies, USA) coupled to an Agilent 5977A MSD forming the same experiments on six different days. The recovery test
detector and an Agilent Enhanced Chemstation and equipped with a CTC was determined by analysing coffee samples at the two concentrations
Combi-Pal autosampler (CTC Analytics AG, Zwingen, Switzerland), with two replicates at each level.
which was configured with a sample tray for 6 20-mL vials. An ADB-
624–30 m column (30 m × 0.25 mm I.D., with a 1.4-μm film thickness; 2.8. Risk assessment of furan and the sum of furan, 2-methylfuran and 3-
J&W Scientific, Folsom, CA, USA) was used. The GC conditions were as methylfuran from coffee products
follows: the initial temperature was 40 ◦ C, which was kept for 2 min, and
subsequently, the temperature was increased at 5 ◦ C per min up to 70 ◦ C, 2.8.1. Coffee consumption data in China
and then it was further increased at 20 ◦ C per min to 210 ◦ C and held for Coffee consumption data were obtained from the China National
10 min at 250 ◦ C. The injector temperature was 250 ◦ C with the split Alcoholic Beverages and Beverages Survey, which was conducted in
ratio of 10:1 and the flow rate of 1.0 mL/min (carrier gas: helium). 2013–2014. This survey used multistage random cluster sampling and
For MSD: MS was operated in electron ionization (EI) mode (70 eV, was conducted in 32 sampling locations in 16 provinces in China. Coffee
230 ◦ C) with a solvent delay of 10 min. Selective ion monitoring (SIM) of consumption was recorded using three discontinuous, face-to-face in­
target ions was performed according to the parameters listed in Table S1 terviews of 24-h diet recalls that were performed on one weekend day
of the supplementary document. (Saturday or Sunday) and two weekdays, and each two adjacent surveys
of the three interviews were conducted at least five days apart. In this
survey, a total of 309 subjects aged 3 to 80 years were coffee consumers.
2.6. Quantification of furan and its derivatives Coffee products included coffee beans, coffee powder (both ground
coffee and instant coffee) and liquid coffee drinks. In addition, a coffee
Cold sodium chloride solution (10 mL, 20% w/w) and 100 μL of company provided the average amount of coffee per customer per day
mixed working internal standard solution (1.0 μg/mL) were added to from the background consumption data. The detailed consumption data
each of the 8 headspace vials. Then, 20, 50, and 100 μL of mixed working for consumers are shown in Tables S5 and S6 of the supplementary
standard solution (0.1 μg/mL) and 20, 50, 100, 200, and 400 μL of mixed document.
working internal standard solution (1.0 μg/mL) were added into each
headspace vial in turn. A cap was placed on the vials without crimping, 2.8.2. Estimation of dietary exposure to furan and the sum of furan, 2-
and the samples were mixed well, corresponding to an internal standard methylfuran and 3-methylfuran from coffee
quantity of 100.0 ng in each vial and a standard quantity between 2.0 The dietary exposure to furan from coffee was calculated by multi­
and 400.0 ng in the vials. A calibration curve was constructed by plot­ plying individual coffee consumption data with corresponding mean
ting the peak area ratio of the analyte and its corresponding internal furan concentrations and summing them. This value was adjusted by the
standard (y axis) against the concentration ratio of the analyte and its measured individual body weight of each consumer (Sui, Zhang, Wu,
internal standard (x axis) using a weighing factor of 1/x. The slope and Song, Yong, Yang, Jiang, & Liu, 2014). Subsequently, the total dietary
the intercept of each curve were calculated using linear regression. exposure to furan was estimated for each consumer. The WHO-

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P. Cao et al. Food Chemistry 387 (2022) 132823

recommended approach was used for undetected values: if the unde­ obtained vials of d5-2-ethylfuran, d3-2,5-dimethylfuran and d11-2-pen­
tected rates were less than 60 %, all the undetected values were assumed tylfuran internal standards each contained 1 mg, which was difficult to
to be LOD/2; in other cases, all the undetected values were assumed to accurately weigh. The concentrations can only be calculated according
be 0 or the LOD (WHO, 1995). to the manufacturer’s label, stating that each vial contained 1 mg, which
Exposure to furan was assessed according to the following formula: resulted in a large difference between the slope of these three internal
∑p standards and the value of 1. However, the accuracy of internal standard
Comik × Conk
Expi = k=1 concentrations had no effects on the results, because the internal stan­
BW i
dards added to the standard solutions and coffee samples were the same.
where Expi denotes the dietary exposure to furan of consumer i from Due to the high contents of furan, 2-methylfuran and 2-ethylfuran in
coffee (μg/kg bw/day); Comik denotes the consumption of consumer i solid coffee products (coffee powder and instant coffee powder), it was
from coffee product k (g/day/person); Conk is the mean concentration of difficult to conduct a low-concentration standard addition analysis. In
furan in coffee product k (μg/kg); Bwi denotes the body weight of con­ this study, low-background coffee product samples were selected to
sumer i (kg); and p is the number of coffee products consumed by con­ analyse the recovery using standard addition method based on furan
sumer i. concentration, and such standard addition analysis was conducted for
In addition, EFSA reported that combination of furan, 2-methylfuran coffee drinks as well. As shown in Table 1, the recoveries and precision
and 3-methylfuran had a dose additivity for hepatotoxicity in rats (EFSA, of the six furan compounds were all satisfied the requirements of this
2017). Hence, the possible contribution of 2-methylfuran and 3-methyl­ method. In addition, the LODs and LOQs of furan and its derivatives in
furan exposure was also assessed, and was adjusted according to the liquid coffee products were 1.5 and 5.0 μg/kg, respectively, whereas
following equation: those in solid coffee products were 6.0 and 20.0 μg/kg, respectively.
MeanTF = MeanF× (1 + Ratio2MF/F + Ratio3MF/F).
MeanTF denotes the mean concentration for the sum of furan, 2- 3.2. Comparison with the US FDA method
methylfuran and 3-methylfuran (μg/kg); MeanF denotes the mean con­
centration for furan (μg/kg); Ratio2MF/F denotes the ratio of 2-methyl­ This method was compared with the US FDA method to analyse the
furan to furan; and Ratio3MF/F denotes the ratio of 3-methylfuran to concentration of furan in coffee beans, coffee powders and coffee drinks.
furan (EFSA, 2017). The results of furan determination in coffee samples obtained by this
Because furan has the potential to induce carcinogenic and genotoxic method and the US FDA method are compared and shown in Table S7.
effects, the MOE approach was applied to assess the human health risk The statistical analysis revealed that there was no significant difference
combined with the exposure results. In our study, both neoplastic and between the furan levels determined in coffee samples by our method
non-neoplastic effects of furan were assessed. For neoplastic effects of and the US FDA method. In addition, Pearson correlation analysis
furan, the benchmark dose lower confidence limit 10% (BMDL10) of showed that there was a strong positive correlation between the two
1.31 mg/kg bw/day was selected to induce hepatocellular adenomas datasets (r = 0.998, P less than 0.001). Compared with the US FDA
and carcinomas in female mice after 2 years of furan administration method, the improved method was easier and more applicable.
(EFSA, 2017; Mayerhofer, Czerwenka, Marchart, Steinwider, & Hof­
staedter, 2019). The BMDL10 at 0.064 mg/kg bw/day was selected for 3.3. Concentrations of furan and its derivatives in coffee products
the non-neoplastic effects of furan, which induced cholangiofibrosis in
male rats after 2 years of furan administration (EFSA, 2017; Mayerhofer, A total of 101 samples of coffee products marketed in China were
Czerwenka, Marchart, Steinwider, & Hofstaedter, 2019). The MOE was analysed. Table 2 describes the levels of the coffee samples analysed,
based on the ratio between BMDL10 and the estimated dietary exposure including the number of coffee samples analysed, the number of
to furan (EFSA, 2017). The MOE value exceeding 10,000 or higher is detected samples (detection rates) and the concentrations of furan and
considered a low public health concern, while MOE value lower than its derivatives in the coffee samples (with more details visualized in a
10,000 represents a potential health concern and requires priority heatmap as demonstrated in Fig. S2). Furan (98%) and 2-methylfuran
management. (100%) had the highest detection rate, followed by 3-methylfuran
(96%), 2-ethylfuran (73%), 2,5-dimethylfuran (86%) and 2-pentylfuran
2.9. Statistical analysis (64%). The statistical analysis revealed that the concentrations of furan
and its derivatives in coffee beans (2080–6569 μg/kg for furan,
Data were analysed using SPSS (Version 25.0 for Windows). The 4780–29639 μg/kg for 2-methylfuran, 234–735 μg/kg for 3-methyl­
concentrations of furan and its derivatives in each sample were furan, 70–378 μg/kg for 2-ethylfuran, 246–1927 μg/kg for 2,5-dimethyl­
measured three times and the average value was taken. The concen­ furan, 35–941 μg/kg for 2-pentylfuran) were significantly higher than
trations of furan and its derivatives are showed as the mean ± standard those in coffee drinks, instant coffee powders and take-away coffee
deviation (SD). (adjusted P<0.005). The concentrations of furan (212–5293 μg/kg), 3-
The significance of the differences in the levels of furan and its de­ methylfuran (33–752 μg/kg), 2-ethylfuran (26–190 μg/kg) and 2-pen­
rivatives in the coffee products was analysed using nonparametric tests tylfuran (7–547 μg/kg) in coffee powders were significantly higher
and Kruskal-Wallis H tests, since the concentration data of furan and its than those in coffee drinks and take-away coffee, whereas the concen­
derivatives did not conform to the normal distribution. A multivariate trations of 2-methylfuran (695–27413 μg/kg) and 2,5-dimethylfuran
data analysis was further implemented by R (Version 4.0.3) to investi­ (52–2236 μg/kg) in coffee powders and instant coffee powders were
gate the potential patterns on the concentrations of furan and its de­ significantly different (adjusted P<0.005). However, no statistically
rivatives, such as the correlation structure. significant differences were observed among coffee beans and coffee
powders. Additionally, the coffee drinks and take-away coffee had the
3. Results and discussion lowest concentrations of furan and its derivatives, but there were no
significant differences between the two coffee products. Studies have
3.1. Method validation shown that furan and its derivatives can be formed during the roasting of
the coffee beans, since their contents were the highest in the roasted
Table S1 shows the calibration curve equations and R2 for furan and coffee beans compared to other coffee products (Van Lancker, Adams,
its derivatives in coffee samples. The R2 values of the calibration curves Owczarek-Fendor, De Meulenaer, & De Kimpe, 2011; Rahn & Yeretzian,
for furan and its derivatives were > 0.999, which indicated a good 2019). Subsequent processing (such as grinding) and brewing resulted in
linearity in the analytical range. In this study, the commercially the loss of the initially generated furan in the coffee beans (Guenther,

4
P. Cao et al. Food Chemistry 387 (2022) 132823

Table 1
Precision and Recovery of furan and its derivatives.
Samples Analytes Concentrations of analytesa Concentration of Standard Average recovery RSDr RSDR
(μg/kg) (μg/kg) (%, n = 6) (%) (%)

Solid coffee products Furan 37.0 40 94.5 7.6 9.2


2-methylfuran 281.0 92.2 9.3 10.4
3-methylfuran 18.5 96.4 6.1 8.6
2-ethylfuran 53.5 97.5 7.2 8.9
2,5-dimethylfuran 10.4 89.4 6.8 9.2
2-pentylfuran ND 92.3 5.6 7.3
Furan 37.0 a400 105.3 5.2 7.3
2-methylfuran 281.0 102.4 7.3 8.4
3-methylfuran 18.5 97.6 4.8 7.6
2-ethylfuran 53.5 95.4 4.2 6.3
2,5-dimethylfuran 10.4 102.3 3.7 6.2
2-pentylfuran ND 102.5 3.1 5.4

Coffee drinks Furan 8.3 20 95.6 6.3 8.4


2-methylfuran 17.8 97.3 7.5 9.7
3-methylfuran ND 98.4 5.2 7.8
2-ethylfuran 10.2 95.9 6.1 8.2
2,5-dimethylfuran ND 96.4 4.2 7.5
2-pentylfuran ND 94.3 5.5 6.1
Furan 8.3 98.4 3.2 7.6
2-methylfuran 17.8 102.4 5.4 8.2
3-methylfuran ND 98.9 2.3 5.4
2-ethylfuran 10.2 200 99.4 4.8 7.4
2,5-dimethylfuran ND 101.3 2.2 4.1
2-pentylfuran ND 102.5 3.4 5.7

ND: not detected;


a
The concentrations of analytes in low background coffee samples;
The LOD, LOQ of furan and its derivatives in liquid coffee products were 1.5 and 5.0 μg/kg, respectively;
The LOD, LOQ of furan and its derivatives in solid coffee products were 6.0 and 20.0 μg/kg, respectively.

Hoenicke, Biesterveld, Gerhard-Rieben, & Lantz, 2010). Thus, coffee furan and its derivatives. Considering that the scale of original con­
beans and coffee powders were the products with the highest contents of centrations varies dramatically in different coffee types, we utilized log-
furan and its derivatives. However, there were no significant differences concentration instead in the analysis for stabilized performance.
between coffee beans and coffee powders in this study, which might be As shown in Fig. 1, a pairs plot (Emerson et al., 2013) can be better
due to the different coffee compositions, origins, and the undetectable highlight the internal structure of the sample data. First, the estimated
small amounts of furan loss during the process of grinding coffee beans density functions showed in the diagonal blocks suggest that log-
to coffee powder for analysis. concentrations of furan and its derivatives are roughly normally
Statistical analysis results showed that the detection rates and con­ distributed with different means and variances in different coffee types.
centrations of furan (98%, ND-6569 μg/kg) and 2-methylfuran (100%, Second, coffee beans and coffee powder share a similar concentration
2–29639 μg/kg) in all coffee samples were significantly higher than distribution for all furan and its derivatives, suggesting that they are
those of other furan derivatives (adjusted Ps<0.0033), which indicated very similar to each other. Third, instant coffee powder has a large
that furan and 2-methylfuran were the dominant residues in coffee distribution variance in all cases, exactly reflecting the large heteroge­
products. No significant differences were found between furan and 2- neity of different instant coffee products in the market. In addition,
methylfuran in any coffee sample. However, the concentration of 2- packed coffee drinks and take-away coffee demonstrate multiple modals
methylfuran in coffee beans and coffee powders was significantly in the concentration distribution of 2,5-dimethylfuran and 2-pentyl­
higher than that of furan (adjusted Ps<0.0033), which was consistent furan, which are also consistent with the facts that these two coffee
with other studies (Chaichi, Mohammadi, & Hashemi, 2013; Fromberg, types contain diverse coffee products. At last, furan and its major de­
Mariotti, Pedreschi, Fagt, & Granby, 2014). Furthermore, the co- rivatives have a linear correlation with each other across most coffee
occurrence of furan, 2-methylfuran, 3-methylfuran and 2,5-dimethylfur­ samples. Both the Pearson / Spearman correlation test to be further
anin coffee was reported in some studies, which was confirmed in this verified such tendency. With the exception of take-away coffee and
study (Leino, Kaitaranta, & Kallio, 1992; Becalski, Hayward, Krakalo­ packaged coffee drinks, partially due to a large proportion of missing
vich, Pelletier, Roscoe, & Vavasour, 2010). Based on the levels of furan data (i.e., not detected) in these two coffee types, most of the correla­
and its derivatives in coffee products, the average 2-methylfuran/furan tions are statistically significant.
ratio, 3-methylfuran/furan ratio and 2,5-dimethylfuran/furan ratio In order to better summarize and compare how the correlation
were calculated to range from 2.5 to 4.5, 0.1 to 0.2 and 0.1 to 0.3, structure of furan and its derivatives varies across different types of
respectively. In addition to furan, 2-methylfuran was the furan deriva­ coffee products, Fig. S3 is showed a group of heatmaps of the correlation
tive with the highest amount of residue in coffee, revealing that the matrix of furan and its derivatives for all samples and samples in
contribution of 2-methylfuran to consumers’ dietary exposure cannot be different types of coffee products. From the Fig. S3, the correlation
ignored. structure of furan and its derivatives keeps a similar pattern across
different coffee types in general. Furthermore, the strength of correla­
3.4. Multivariate data analysis tion decreases uniformly after we broke down the samples into groups
defined by coffee types, suggesting that group-level analysis makes more
Fig.S2 reveals that the 5 coffee types have very different patterns on sense for heterogonous data as considered here. Correlation among
the concentrations of furan and its derivatives. In this subsection, a furan and its derivatives tends to become weaker from primary coffee
multivariate data analysis was implemented to further investigate these products such as coffee beans and powder to deep-processing products
heterogonous patterns and the potential correlation structure of the like instant coffee powder and packages of coffee drinks. In addition, the

5
P. Cao et al.
Table 2
Concentrations of furan and its derivatives in coffee product samples on Chinese market.
Products Samples Concentrations of Samples Concentrations of 2- Samplesdetecteda Concentrations Samples Concentrations Samples detecteda Concentrations of Samples Concentrations
detecteda furan in samples b detecteda (2- methylfuran in (3-methylfuran) of 3-methylfuran detecteda (2- of 2-ethylfuran (2,5- 2,5-dimethylfuran detecteda (2- of 2-pentylfuran
(Furan) (μg/kg) methylfuran) samples b in samples b ethylfuran) in samples b dimethylfuran) in samples b pentylfuran) in samples b
(μg/kg) (μg/kg) (μg/kg) (μg/kg) (μg/kg)

Mean Range Mean Range Mean Range Mean Range Mean Range Mean Range

Packaged 29 39 ± ND-152 31 97 ± 2.1–449 27 3.8 ± ND-9 15 1.3 ± 1–3 20 3.9 ± ND-16 3 1.7 ± ND-19
coffee (94%) 38cde (100%) 101de (87%) 2.0def (48%) 0.7de (65%) 3.6de (10%) 3.8de
drinks
Coffee 19 2686 ± 212–5293 19 12098 695–27413 19 328 ± 33–752 19 103 ± 26–190 19 811 ± 52–2236 19 172 ± 7–547
powder (100%) 1153df (100%) ± (100%) 154dh (100%) 34dg (100%) 548dfh (100%) 145df
7084dfh
Coffee 27 4314 ± 2080–6569 27 15903 4780–29639 27 443 ± 234–735 27 141 ± 70–378 27 1021 246–1927 27 244 ± 35–941
beans (100%) 1398egh (100%) ± (100%) 134egi (100%) 62efh (100%) ± (100%) 191egh
7215egi 494egi
6

Instant 13 298 ± 9–1791 13 1223 ± 59–4436 13 47 ± 10–163 13 29 ± 14–46 12 67 ± ND-216 13 7.4 ± 2–23
coffee (100%) 477 h (100%) 1447hi (100%) 46 fg (100%) 10fi (92%) 81 fg (100%) 6.6 h
powder
Take-away 11 59 ± 25 30–108 11 215 ± 86–375 11 3.6 ± 2–7 0 0.8 ± ND 8 3.8 ± ND-12 3 1.7 ± ND-7
fg
coffee (100%) (100%) 96 fg (100%) 1.3hi (0%) 0.0ghi (73%) 3.8hi (27%) 2.0 fg

Total 99 1715 ± ND-6569 101 6738 ± 2–29639 97 188 ± ND-752 74 61 ± ND- 87 436 ± ND-2236 65 99 ± ND-
(98%) 2052 (100%) 8560 (96%) 218 (73%) 70 378 (86%) 578 (64%) 158 941

ND: not detected;


The LOD, LOQ of furan and its derivatives in liquid coffee products were 1.5 and 5.0 μg/kg, respectively; the LOD, LOQ of furan and its derivatives in solid coffee products were 6.0 and 20.0 μg/kg, respectively;
a
Greater than or equal to the LOD; The number of samples positive for furan and its derivatives, with detection rate (%) in parentheses;
b
Levels less than LOD were considered as 1/2 LOD during calculation of mean;
c
Mean ± Standard deviation;
d,e,f,g,h,I
The levels of furan and its derivatives in the five coffee products were significantly different (adjusted P<0.005).

Food Chemistry 387 (2022) 132823


P. Cao et al. Food Chemistry 387 (2022) 132823

Fig. 1. Exploratory data analysis on log-concentration of furan and its five major derivatives in 5 types of coffee products. Marginal distributions of log-concentration
of furan and its derivatives in different product types are visualized in the diagonal blocks, with different product types highlighted in different colors. Scatterplots of
each pair of furan compounds are illustrated in the left-bottom blocks. Pearson correlations of two furan and its derivatives throughout all samples (grey color) and
within different product types (other colors) are reported in the right-up blocks.

cluster analysis was also performed. The 101 coffee products were frequency and volume of liquid coffee might be the reason that liquid
clustered into five clusters using the Euclidean metric with the average coffee was the main contributor to furan and its derivatives. Further­
linkage method. The results were consistent with those obtained from more, some Chinese parents may buy the packaged coffee drinks for
the manual labeling (Fig. S4, Table S8). children, since some packaged coffee drinks tasted better with milk and
sugar (Tao, Hao, Lu, Tian, &Feng, 2015). Due to the lower body weight
of children, the exposure levels of furan and its derivatives per kilogram
3.5. Exposure to furan and the sum of furan, 2-methylfuran and 3-
body weight were higher. In addition, for the take-out coffee consumers,
methylfuran from coffee consumption
>99% of consumers’ exposure to furan and the sum of furan, 2-methyl­
furan and 3-methylfuran ranged from 0.01 to 0.04 μg/kg bw/day and
The dietary exposures to furan and the sum of furan, 2-methylfuran
0.05 to 0.18 μg/kg bw/day, respectively, while 0.1% or less of consumer
and 3-methylfuran in coffee products on the Chinese market are shown
exposure to furan and the sum of furan, 2-methylfuran and 3-methyl­
in Table 3. Considering the realistic transfer rates of furan from coffee
furan ranged from 0.11 to 2.42 μg/kg bw/day and 0.50 to 11.38 μg/
beans and coffee powders to a cup of coffee for consumption, a pro­
kg bw/day, respectively (Table 4). Lattes, mochas, and cappuccinos
cessing factor of 50% furan (brewing process) and its derivatives was
were the largest contributors to furan exposure for Chinese take-out
used to calculate the daily intake and MOE (La Pera, Liberatore, Avel­
coffee consumers, possibly due to the habits of Chinese coffee
lone, Fanara, Dugo, & Agozzino, 2009; Guenther, Hoenicke, Biesterveld,
consumers.
Gerhard-Rieben, & Lantz, 2010). In addition, for the liquid coffee drinks
In 2017, the EFSA published results of the dietary exposure to furan
(including take-away coffee and packaged coffee drinks), 10% loss rate
in a European population. The daily exposure to furan was between 0.11
of furan and its derivatives was used to calculate the daily intake and
and 0.65 μg/kg bw/day for children and adolescents and between 0.11
MOE (Guenther, Hoenicke, Biesterveld, Gerhard-Rieben, & Lantz, 2010;
and 0.75 μg/kg bw/day for adults, while coffee was the major contrib­
Han, Kim, & Lee, 2017). The average dietary exposures of furan and the
utor to furan exposure for adults (EFSA, 2017). However, the dietary
sum of furan, 2-methylfuran and 3-methylfuran from coffee products in
exposure to furan in this study was lower than that in the EFSA study
Chinese consumers were 0.09 and 0.46 μg/kg (body weight (bw))/day,
because the food category was only coffee in our study. The estimated
respectively (Table 3). At P95, exposures were estimated to be 0.25 μg/
dietary intake of furan (from food categories including flour and flour
kg bw/day (furan) and 1.32 μg/kg bw/day (the sum of furan, 2-methyl­
products, tubers, vegetables, salted vegetables, fruits, nuts, milk and
furan and 3-methylfuran) for coffee consumers. The mean dietary
milk products and seasonings) was 0.093 μg/kg bw/day in the Chinese
exposure to furan and the sum of furan, 2-methylfuran and 3-methyl­
adults population (Wu et al., 2014). Considering the exposure to furan
furan in different age groups ranged from 0.07 to 0.09 μg/kg bw/day
from other foods, it is estimated that the mean dietary exposure to furan
and 0.32 to 0.48 μg/kg bw/day, respectively, whereas that in groups
was approximately 0.18 μg/kg bw/day for adult coffee consumers in
with high exposure (P95) ranged from 0.13 to 0.25 μg/kg bw/day and
China. Furthermore, exposure to furan in coffee products is lower than
0.62 to 1.41 μg/kg bw/day, respectively. The exposure to furan and the
that in other countries (Morehouse, Nyman, McNeal, Dinovi, & Perfetti,
sum of furan, 2-methylfuran and 3-methylfuran in Chinese consumers
2008; Altaki et al., 2011; EFSA, 2017). In the latest Australian assess­
was mainly contributed by liquid coffee drinks, whereas the second
ment study, the mean daily intake of furan from coffee products was
highest contributor for exposure to furan and its derivatives for Chinese
0.251 μg/kg bw/day for adults, which is approximately 2.8 times that of
adults comes from coffee powder (Fig. 2). In this study, approximately
adults in China (Mayerhofer, Czerwenka, Marchart, Steinwider, &
35% of the 309 coffee consumers bought coffee beans (1%) and coffee
Hofstaedter, 2019). In addition, the exposure of adolescents to furan in
powders (34%, including instant coffee powders) to make coffee bev­
this study was mainly from liquid coffee, which was consistent with
erages. The majority of coffee consumers purchased liquid coffee
other studies and lower than that in other Western countries (Waize­
products directly from vendors (including packaged coffee drinks and
negger, Winkler, Kuballa, Ruge, Kersting, Alexy, & Lachenmeier, 2012).
take-away coffees), accounting for 75%. The higher consumption in

7
P. Cao et al. Food Chemistry 387 (2022) 132823

Different dietary behavior might be the main reason for the differences

103–356
34–6400
19–6400
19–6400
between furan exposures from coffee in China and other countries.

Range
According to the calculation of MOEs for the neoplastic effects of
furan, the MOEs were more than the threshold of 10,000 for the mean
exposure estimates (14556), while they were below the 10,000 for the

—□
P95

103
95th percentile exposure estimates (P95) (5240). The MOEs ranged from

45
48
14,556 to 18,714 for the mean dietary exposure of subgroups. In addi­
MOE b*

The loss rate of furan and its derivatives was 50% from coffee bean and coffee powder to the cup of coffee for consumption; loss rate of furan and its derivatives was 10% for liquid coffee drinks;
tion, according to the calculation of MOEs for the non-neoplastic effects
Mean

160
200
133
139
of furan, the MOEs were 711 and 256 for the mean and the P95 exposure
estimates, respectively, while 139 and 48 were considered to be the sum
of furan, 2-methylfuran and 3-methylfuran from coffee products. The
Dietary exposure to the sum of furan, 2-methylfuran and

MOEs ranged from 711 to 914 for the mean dietary exposure of sub­
groups and from 133 to 200 for the sum of furan, 2-methylfuran and 3-
methylfuran. Furthermore, the calculation of MOEs for the neoplastic
effects of furan was > 10,000 for the > 99% take-out coffee consumers
but fewer than 10,000 for the less than 1% of consumers. However, the
3-methylfuran from coffee products d

MOE values calculated were less than 10,000 for the neoplastic effects of
furan and the sum of furan, 2-methylfuran and 3-methylfuran. There­
0.18–0.62
0.01–1.86
0.01–3.32
0.01–3.32

fore, due to the neoplastic effects and non-neoplastic effects of furan,


Range

coffee consumers with MOEs below 10,000 indicated a health concern.

3.6. Uncertainty analysis


(μg/kg bw/day)

0.62
1.41
1.32
—□
P95
Estimation of dietary exposure to furan, the sum of furan, 2-methylfuran and 3-methylfuran and MOEs from coffee products on Chinese market.

The sum of furan, 2-methylfuranand 3-methylfuran was calculated based on the equation, MeanTF = MeanF × (1 + Ratio2MF/F + Ratio3MF/F).

Some uncertainties in this study may influence the estimated expo­


sure to furan. Firstly, only coffee products were studied, which may
Mean

0.40
0.32
0.48
0.46

cause underestimation of furan exposure from other food categories,


MOE a was calculated based on the neoplastic effects of furan and MOE b was calculated based on the non-neoplastic effects of furan;

such as heat-treated foods. Secondly, the carcinogenic mode of action of


194–45714
107–42667
107–45714

furan may result in an underestimation of the actual exposure, and an


492–1600

additive approach for furan and methylfurans regarding hepatotoxicity


Range

causes potential uncertainties in this study. Thirdly, due to the high


Levels less than LOD were considered as 1/2 LOD during calculation of dietary exposure to furan from coffee products;

volatility of furan, theoretical loss rates for furan and its derivatives for
liquid coffee drinks (10%) and solid coffee (50%) were applied to
P95

492
256
256

calculate their daily exposure and MOE values in this study. Indeed, the
loss rates of furan and its derivatives in coffee products can be influenced
MOE b

Mean

711
914
711
711

by a variety factors in the actual consumption of coffee, such as the


subsequent processing steps (storage, grinding, degassing), shelf-life,
and consumer handling (brewing time and temperature, processing
10077–32750
3970–935714
2183–873333
2183–935714

* denoted the MOEs for the sum of furan, 2-methylfuran and 3-methylfuranfrom coffee products;

with domestic coffee machine) (Guenther, Hoenicke, Biesterveld,


Gerhard-Rieben, & Lantz, 2010). Furthermore, due to the loss rates of
Range

furan and its derivatives in coffee products were not studied, which also
brings some limitations in this study.
10,077
5240
5240
—□

4. Conclusion
P95

The current study determined the concentrations of furan and its


14,556
18,714
14,556
14,556
MOE a

Mean

major furan derivatives, which may have the similar metabolic, carci­
nogenic and genotoxic effects in coffee products on the Chinese market
using the improved HS-GC–MS method and estimated their potential
c

health risks on Chinese coffee consumers. The current improved


Dietary exposure to furan from coffee products

method, which has more applicability and is easier to operate compared


to the US FDA method, detected furan and its five major derivatives.
Coffee in the forms of beans and powders had the highest levels of furan
and its derivatives. Among furan and its derivatives, furan and 2-meth­
0.0014–0.33
0.0015–0.60
0.0014–0.60

ylfuran were the compounds with the highest concentrations and


0.04–0.13

detection rates in all coffee products. In Chinese consumers, the mean


Range

dietary exposures of furan and the sum of furan, 2-methylfuran and 3-


methylfuran in coffee products were 0.09 and 0.46 μg/kg bw/day,
(μg/kg bw/day)

respectively. For the neoplastic effects of furan, the MOE was 14,556 for
0.13
0.25
0.25
—□
P95

the mean dietary exposure of consumers, which means that general


coffee consumers had a lower health concern. However, with regard to
Mean

0.09
0.07
0.09
0.09

the non-neoplastic effects of furan, MOEs were 711 and 139 for furan
and the sum of furan, 2-methylfuran and 3-methylfuran, respectively. A
P, percentile;

health concern was indicated for coffee consumers (especially con­


Consumers

sumers consuming large amounts of coffee), with MOEs below 10000.


Table 3

Group

7–17

Therefore, it is suggested that Chinese coffee consumers may modify


≥18
3–6

their dietary behaviour towards consuming coffee to limit the exposure


d
c

8
P. Cao et al. Food Chemistry 387 (2022) 132823

Fig. 2. Exposure to furan (A) and the sum of furan, 2-methylfuranand 3-methylfuran (B) in coffee products of different age groups.

Table 4
Estimation of dietary exposure to furan, the sum of furan, 2-methylfuran and 3-methylfuran and MOEs for take-out coffees.
Take-out Dietary exposure to furan MOE a MOE b Dietary exposure to the sum MOE b*
coffees from take-out coffees c (μg/ of furan, 2-methylfuran and
kg bw/day) 3-methylfuran d
(μg/kg bw/day)

≥99% ≤0.1% ≥99% ≤0.1% ≥99% ≤0.1% ≥99% ≤0.1% ≥99% ≤0.1%
consumers consumers consumers consumers consumers consumers consumers consumers consumers consumers

Cafe 0.02 0.86 75,138 1521 3671 74 0.08 4.05 780 16


Americano
Latte, Mocha, 0.04 2.42 33,718 542 1647 26 0.18 11.38 350 6
Cappuccino
Espresso 0.01 0.20 133,354 6478 6515 316 0.05 0.95 1384 67
Cold brew iced 0.01 0.18 121,330 7285 5928 356 0.05 0.85 1259 76
coffee
Pour over, drip 0.02 0.11 63,803 12,397 3117 606 0.10 0.50 662 129
coffee

The loss rate of furan and its derivatives was 10% for liquid coffee drinks;
MOE a was calculated based on the neoplastic effects of furan and MOE b was calculated based on the non-neoplastic effects of furan;
* denoted the MOEs for the sum of furan, 2-methylfuran and 3-methylfuran from take-out coffees;
c
The average concentrations of furan, 2-methylfuran and 3-methylfuran (59 μg/kg, 215 μg/kg, 4 μg/kg) were used to calculate dietary exposure to furan and the sum
of furan, 2-methylfuran and 3-methylfuran;
d
The sum of furan, 2-methylfuran and 3-methylfuran was calculated based on the equation, MeanTF = MeanF × (1 + Ratio2MF/F + Ratio3MF/F).

to furan and its derivatives. In particular, the parents should limit the Declaration of Competing Interest
children from coffee consumption. Future research on the coffee in­
dustry should be further conducted in order to control the levels of furan The authors declare that they have no known competing financial
and its derivatives in coffee products through an adequate thermal interests or personal relationships that could have appeared to influence
processing and volatilization. the work reported in this paper.

Funding Appendix A. Supplementary data

This work was supported by the Department of Ministry of Science Supplementary data to this article can be found online at https://doi.
and Technology of the People’s Republic of China [grant number org/10.1016/j.foodchem.2022.132823.
2018YFC1603600], CIFST Food Science and Technology Fund-Abbott
Food Nutrition and Safety Special Research Fund (201911003) and References
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