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Exposure risk to carbonyl compounds and furfuryl alcohol through the consumption of sparkling wines/Risco da exposicao a compostos carbonilicos e alcool furfurilico atraves do consumo de espumantes.

Furfuryl alcohol (FA) and carbonyl compounds, including acetaldehyde, acrolein, formaldehyde, furfural and ethyl carbamate may form adducts with the DNA due to their electrophilic nature. As consequence, the exposure to furfuryl alcohol (SACHSE et al., 2016), acetaldehyde (ERIKSSON, 2015) and ethyl carbamate (LIU et al., 2017), for example, may increase the risk of cancer in some parts of the human organism, including liver and kidneys. Furthermore, these compounds may be associated with some particular toxic effects, such the relation between formaldehyde and arthritis (OSMAN et al., 2017) and acrolein that play an important role in Parkinson's (AMBAW et al., 2018) and Alzheimer's diseases (BURCHAM, 2017). Furfural toxicity still needs to be better studied, but it is suspected of being a mutagen and might be associated with liver neoplasms (hepatocellular adenomas or carcinomas) (ARTS et al., 2004).

These compounds may be formed from sugars and amino acids, especially during fermentation (RIBEREAU-GAYON et al., 2006). In addition, acrolein and furfural may be released to the environment and contaminate grapes during incomplete combustion processes (petrochemical fuels, wood, cigarette smoking among others) (KENNISON et al., 2007; BURCHAM, 2017). In a previous study, the occurrence of carbonyl compounds (formaldehyde, acetaldehyde, acrolein, furfural and EC) was reported in all stages of vinification, including grapes and the respective wines (FERREIRA et al., 2018). However, toxic levels were reduced throughout Merlot vinification and only the exposure to acrolein revealed represent risk to consumer's health. In another approach, LAGO et al. (2017) verified that the advancement of ripeness degree and increasing grape maceration time seems to result in higher concentrations of these carbonyl compounds in Syrah wines. Regarding the consumption of these wines, the exposure to acrolein and ethyl carbamate could pose risk to consumer health.

The occurrence of FA and carbonyl compounds (acetaldehyde, acrolein, EC, formaldehyde and furfural) was studied in this research with the objective of verifying, for the first time, the risk of exposure to these compounds through consumption of sparkling wines. Sparkling wines from 21 different wineries of Rio Grande do Sul State, Brazil, were evaluated. Samples were analyzed in triplicate and total acidity, pH and alcohol content were verified according the ASSOCIATION OF OFFICIAL AGRICULTURAL CHEMISTIS (1995), since these parameters can influence the efficiency of HS-SPME (FERREIRA et al., 2019). The median values of acidity (108meq [L.sup.-1]), pH (3.1) and alcohol (12%) of samples were used in the preparation of the model solution of sparkling wine to perform the calibration curves of toxic compounds. This approach was followed to minimize matrix effects in the analysis quantification.

The estimated daily intake (EDI) and characterization of the exposure risk were obtained following the protocols of the World Health Organization (WHO, 2010),as reported in previous studies (LAGO et al., 2017; FERREIRA et al., 2018; DACHERY et al. 2017). The EDI was expressed in [micro]g [kg.sup.-1] of body weight (BW) per day and calculated as follows:

EDI = [concentration of toxic compound ([micro]g [mL.sup.-1]) x sparkling wine consumption (mL [day.sup.-1])]/ body weight (kg)]

The concentration of toxic compounds was obtained through headspace solid phase microextraction associated with gas chromatography with quadrupole mass spectrometric detection in selected-ion monitoring mode (HS-SPME-GC/ qMS-SIM) according previous validated method (FERREIRA et al., 2019).

The consumption of sparkling wine used in the calculation of EDI was 300mL, considering that: (i) the maximum daily alcohol intake should not exceed 30g (equivalent to 39mL of ethanol), as established by the Health Agencies of several countries, including the United States of America, France, Macedonia, New Zealand, Romania, Switzerland, Uruguay and released by the International Alliance for Responsible Drinking (IARD, 2018), and that (ii) the evaluated sparkling wines presented ethanol content between 11.5 and 12.5% (v/v). Furthermore, VAZQUEZ-AGELL et al. (2007) reported that daily consumption of 300mL of Chardonnay sparkling wine may prevent atherosclerosis due to its polyphenol content.

The Brazilian average weight of 66.5kg, according to Analysis of Personal Food Consumption done by Brazilian government (IBGE, 2011), was used in the EDI calculation.

Acetaldehyde, acrolein, formaldehyde and ethyl carbamate are genotoxic compounds and margin of exposure (MOE) must be used in risk characterization considering the benchmark dose lower confidence limit (BMDL10) as toxicological parameter in the in the calculation:

MOE = BMDL10 ([micro]g [kg.sup.-1] BW [day.sup.-1])/ EDI ([micro]g [kg.sup.-1] BW [day.sup.-1])

BMDL10 corresponds to the lowest limit of the 95% confidence interval of the dose required to give a 10% increase in the occurrence of a toxic effect compared to the control. BMDL10 values were: 56, 0.36, 0.25 and 28mg [kg.sup.-1] of body weight per day were used for acetaldehyde (LACHENMEIER et al., 2009), acrolein (ATSDR, 2007), EC (SCHLATTER et al., 2010) and formaldehyde (MONAKHOVA et al., 2012), respectively, as already mentioned in a previous study (FERREIRA et al. 2018).

MOE values below 10,000 indicated that the compound poses a potential health risk (WHO, 2010). In contrast, furfural and furfuryl alcohol are non-genotoxic compounds; and therefore, has a safe ingestion parameter set by JECFA (acceptable summative daily intake (ADI) of 500pg [kg.sup.-1] BW) (JECFA, 2000). Risk characterization for these two furan-containing compounds was carried out comparing the EDI with its ADI, where risk may exist if the estimated intake exceeds the ADI.

Carbonyl compounds and furfuryl alcohol were reported in all samples. Table 1 presents the levels, EDI and MOE of these compound found in sparkling wines under study. EC and formaldehyde were not included in table 1, as these compounds were found at low levels in all samples (not quantifiable since these values were between the LOD and LOQ of the method, 0.4 and 1[micro]g [L.sup.-1], respectively for both compounds), indicating no risk to consumer health. The occurrence of these compounds was reported for the first time in sparkling wines in the present study. The same exposure risk assessment approach adopted for the samples under study was used to verify if the levels of these compounds reported in the literature would pose a risk to consumers' health. In still wines, EC was reported, for example, in samples from China (13.7[micro]g [L.sup.-1]) (ZHANG et al 2014) and Portugal (54.1[micro]g [L.sup.-1]) (PERESTRELO et al. 2010), which exposure would result in MOE values of 4167 and 1042, respectively; and therefore, with health risk potential according to the threshold of World Health Organization (MOE<10,000) (WHO, 2010). Formaldehyde was found in wines from South Korea and Germany at average levels of 40.9[micro]g [L.sup.-1] (JEONG et al. 2015) and 130[micro]g [L.sup.-1] (JENDRAL et al. 2011), resulting in MOE values of 155,556 and 47,457, respectively; i.e., with no potential for risk to health.

Acetaldehyde, furfural and acrolein were also reported at low levels (concentrations lower than LOQ of the method: 1.5, 1.4 and 1.0[micro]g [L.sup.-1] and higher than LOD: 0.8; 0.5 and 0.7[micro]g/Lin 57, 71 and 76% of samples, respectively), which do not pose a health risk. In the other samples, the levels of acetaldehyde and furfural ranged from 5.2 to 50.5 and 10.5 to 41[micro]g [L.sup.-1], respectively (Table 1). Levels of these compounds were used for the calculation of the possible exposure, resulting in low EDI ranging from 0.023 to 0.247 and 0.047 to 0.185[micro]g [kg.sup.-1] of BW for acetaldehyde and furfural, respectively. Since acetaldehyde is genotoxic, the MOE was used to characterize the risk, which presented values higher than 10,000 (ranging from 2,387,179 to 226,521, as shown in table 1), indicating that the exposure to this aldehyde does not pose a health risk.

In the case of furfural (non-genotoxic), the EDI has also indicated no health risk, since EDI was lower than the ADI established by JECFA (2000). The same was verified for furfuryl alcohol found at levels from 10.4 to 42[micro]g [L.sup.-1], which correspond to EDI of 0.047 to 0.189[micro]g [kg.sup.-1] of BW, respectively; and therefore, also lower than the ADI (500pg [kg.sup.-1] of BW). Regarding the occurrence of these compounds reported in literature, only acetaldehyde was previously verified in sparkling wines (WEBBER et al., 2017), which levels was higher (up 60mg [L.sup.-1], which indicate risk for consumers' health) than those reported in this study.

Levels (20.3 to 36.7 [micro]g [L.sup.-1]) and EDI (0.092 to 166[micro]g [kg.sup.-1] of BW) of acrolein found in 24% of the samples under study were sufficient to represent risk to health (MOE values between 3931 and 2174, respectively; i.e, lower than WHO threshold (10,000) (WHO, 2010). This aldehyde was reported for the first time in sparkling wine and has rarely been evaluated in still wines in the literature. In still wines from South African, BAUER et al. (2012) have not detected acrolein and in German wines. KACHELE et al. (2015) reported acrolein in still wines at lower levels (0.7[micro]g [L.sup.-1]) than those verified in this study; and therefore without potential to cause health risk (MOE: 120,000 obtained using the same exposure approach adopted for the sparkling wines under study).

Levels of acetaldehyde, EC, formaldehyde, furfural and furfuryl alcohol reported in all sparkling wines do not pose a risk to the health of consumers. However, the occurrence of acrolein deserves attention. This compound was the only whose exposure indicates concern due to the levels detected and its possibility of reacting with the biological nucleophilic targets such as proteins, RNA and DNA, causing cellular dysfunction and/or mutagenicity. In our previous studies, acrolein was found in still wines elaborated using Syrah grapes from Sao Francisco Valley (LAGO et al., 2017) and Merlot from Campanha Gaucha (FERREIRA et al., 2018) in sufficient quantities to result risk to human health. This compound was also present in grapes used to winemaking (FERREIRA et al., 2019). Therefore, the environmental contamination of grapes with acrolein due to incomplete combustion processes (petrochemical fuels and wood) or photo oxidation of hydrocarbon found in air may be related the occurrence of this aldehyde in wines.

The role of precursors, fermentation, type of sparkling and storage in the acrolein levels should be elucidated to predict strategies focused on reducing the occurrence of this compound. In addition, it is important to mention that the evaluation of levels of carbonyl compounds and furfuryl alcohol, as well as the monitoring of levels of ochratoxin A and pesticide residues can be important tools for the quality control of wines.

http://dx.doi.org/ 10.1590/0103-8478cr20180986

Received 11.29.18

Approved 02.07.19

Returned by the author 03.08.19

CR-2018-0986.R1

ACKNOWLEDGEMENTS

This study was funded by National Council of Technological and Scientific Development (Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq), CNPq project Pq 425755/2016-9), the Coordination for the Improvement of Higher Education Personnel, Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES) and Research Support Foundation of Rio Grande do Sul (Fundacao de Amparo a Pesquisa do Estado do Rio Grande do Sul (FAPERGS), Edital Pesquisador Gaucho, Project 1995-2551/13-7).

DECLARATION OF CONFLICT OF INTERESTS

The authors declare no conflict of interest. The founding sponsors had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and in the decision to publish the results.

AUTHORS' CONTRIBUTIONS

The authors contributed equally to the manuscript.

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Gabriela Pelizza Peterie (1) Karolina Cardoso Hernandes (1) Luana Schmidt (1) Julia Barreto Hoffmann Maciel (1) Claudia Alcaraz Zini (2) Juliane Elisa Welke (1)* (iD)

(1) Instituto de Ciencia e Tecnologia de Alimentos (ICTA), Universidade Federal do Rio Grande do Sul (UFRGS), 91501970, Porto Alegre, RS, Brasil. E-mail:juliane.welke@ufrgs.br.* Corresponding author.

(2) Instituto de Quimica (IQ), Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS, Brasil.
Table 1--Levels [+ or -] standard deviation ([micro]g [L.sup.-1]),
estimated daily intake (EDI, [micro]g [kg.sup.-1] of body weight)
and margin of exposure (MOE, calculated only for genotoxic compounds
including acetaldehyde and acrolein) of the toxic compounds reported
in the sparkling wines analyzed by HS-SPME-GC-MS-SIM. EC and
formaldehyde were not included in the Table, since these compounds
were found at levels between the LOD and LOQ of the method (0.4 and
1[micro]g [L.sup.-1], respectively, for both compounds) in all
samples.

                         Acetaldehyde

N. (a)         Level          EDI       MOE

1        <LOQ                <0.007   >8331096
2        <LOQ                <0.007   >8331096
3        <LOQ                <0.007   >8331096
4        <LOQ                <0.007   >8331096
5        12.4 [+ or -] 0.0   0.056    1001075
6        50.5 [+ or -] 1.7   0.228    245809
7        <LOQ                <0.007   >8331096
8        37.9 [+ or -] 3.7   0.171    327529
9        <LOQ                <0.007   >8331096
10       31.1 [+ or -] 0.8   0.140    399143
11       <LOQ                <0.007   >8331096
12       <LOQ                <0.007   >8331096
13       <LOQ                <0.007   >8331096
14       30.5 [+ or -] 8.7   0.138    406995
15       <LOQ                <0.007   >8331096
16       5.2 [+ or -] 1.6    0.023    2387179
17       15.1 [+ or -] 4.0   0.068    822075
18       54.8 [+ or -] 8.9   0.247    226521
19       <LOQ                <0.007   >8331096
20       <LOQ                <0.007   >8331096
21       10.2 [+ or -] 1.6   0.046    1216993

                       Acrolein

N. (a)         Level          EDI      MOE

1        <LOQ                <0.009   >40101
2        <LOQ                <0.009   >40101
3        <LOQ                <0.009   >40101
4        <LOQ                <0.009   >40101
5        <LOQ                <0.009   >40101
6        33.1 [+ or -] 1.7   0.149    2411
7        <LOQ                <0.009   >40101
8        33.4 [+ or -] 0.3   0.151    2389
9        <LOQ                <0.009   >40101
10       <LOQ                <0.009   >40101
11       <LOQ                <0.009   >40101
12       <LOQ                <0.009   >40101
13       <LOQ                <0.009   >40101
14       28 [+ or -] 1.8     0.126    2850
15       <LOQ                <0.009   >40101
16       <LOQ                <0.009   >40101
17       <LOQ                <0.009   >40101
18       36.7 [+ or -] 3.0   0.166    2174
19       20.3 [+ or -] 2.4   0.092    3931
20       <LOQ                <0.009   >40101
21       <LOQ                <0.009   >40101

                    Furfural                 Furfuryl alcohol

N. (a)         Level          EDI            Level           EDI

1        <LOQ                <0.006   15.8 [+ or -] 2.0     0.071
2        <LOQ                <0.006   11.1 [+ or -] 0.1     0.050
3        12.9 [+ or -] 0.1   0.058    42 [+ or -] 3.9       0.189
4        <LOQ                <0.006   14.4 [+ or -] 0.8     0.065
5        <LOQ                <0.006   13.7 [+ or -] 1.4     0.062
6        15.6 [+ or -] 3.3   0.070    15.8 [+ or -] 1.7     0.071
7        <LOQ                <0.006   14.4 [+ or -] 1.7     0.065
8        41.0 [+ or -] 0.4   0.185    13.9 [+ or -] 0.8     0.063
9        <LOQ                <0.006   11.9 [+ or -] 0.7     0.054
10       32.1 [+ or -] 0.3   0.145    17.9 [+ or -] 0.5     0.081
11       <LOQ                <0.006   13.4 [+ or -] 0.3     0.060
12       <LOQ                <0.006   16.2 [+ or -] 0.6     0.073
13       <LOQ                <0.006   13.6 [+ or -] 0.2     0.061
14       14.4 [+ or -] 3.0   0.065    15.5 [+ or -] 0.6     0.070
15       <LOQ                <0.006   21. 9 [+ or -] 1.7    0.099
16       <LOQ                <0.006   17.8 [+ or -] 0.3     0.080
17       <LOQ                <0.006   14.2 [+ or -] 1.0     0.064
18       10.5 [+ or -] 3.4   0.047    20.3 [+ or -] 3.4     0.092
19       <LOQ                <0.006   22.5 [+ or -] 2.9     0.102
20       <LOQ                <0.006   10.4 [+ or -] 1.7     0.047
21       <LOQ                <0.006   33.5 [+ or -] 4.0     0.151

(a) Sample number.

LOQ: limit of quantification of HS-SPME-GC/MS-SIM method for
acetaldehyde, furfural and acrolein was 1.5, 1.4 and 1.0[micro]g
[L.sup.-1], respectively, according to the validation procedure
previously reported by Ferreira et al. (2019).
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Title Annotation:FOOD TECHNOLOGY
Author:Peterle, Gabriela Pelizza; Hernandes, Karolina Cardoso; Schmidt, Luana; Maciel, Julia Barreto Hoffma
Publication:Ciencia Rural
Date:Mar 1, 2019
Words:4069
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