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Stable Carbon Isotopic Composition Indicates Large Presence of Maize in Brazilian Soy Sauces (Shoyu)
Stable Carbon Isotopic Composition Indicates Large Presence of Maize in Brazilian Soy Sauces (Shoyu)
Stable Carbon Isotopic Composition Indicates Large Presence of Maize in Brazilian Soy Sauces (Shoyu)
Short Communication
A R T I C LE I N FO A B S T R A C T
Keywords: Carbon and nitrogen (N) isotopic compositions were used to test the presence of C4 carbon in soy sauces (shoyu)
Shoyu produced in Brazil. Seventy samples of Brazilian shoyu were analyzed and compared with the same product from
Sauce Japan, China, Singapore, Taiwan, and United States. The average ( ± standard-deviation) δ13C of the Brazilian
Soy shoyu was −15.0 ± 3.4. The average ( ± standard-deviation) δ13C of five shoyu samples from Japan was
Maize
−25.2 ± 0.6‰. The δ13C of shoyu from US (−25.3‰) and Singapore (−25.9‰) were close to Japanese
Stable isotopes
samples. Shoyu δ13C values from China were equal to −20‰ and −15.4‰, and from Taiwan equal to −20.2‰.
Brazil
Food analysis The average δ15N value of Brazilian shoyu was 0.3 ± 1.2‰. The variability of δ15N values among shoyu from
Food composition other countries was much lower than Brazilian shoyu, and the average was 1.4 ± 0.3‰. Using a simple isotopic
mass balance, we estimated that most of the shoyu in Brazil contains < 20% soy, and the dominant cereal is
maize, probably because in Brazil maize is cheaper than soybean.
1. Introduction produced, which is more than the production of mustard and pepper
sauces combined (FAOSTAT, 2017).
Brazil has the largest community of Japanese people outside Japan. Brazilian legislation defines shoyu as the product of the fermentation
There are 400.000 Japanese, and 1.5 million including their descen- of soy and other cereals, including maize, rice and wheat. Soy, rice and
dants in the country (BRAZIL, 2017). The first wave of Japanese im- wheat are plants that follow the C3 photosynthetic pathway, while
migrants arrived on board the ship Kasato Maru in 1908. After a cen- maize follows the C4 pathway. The stable carbon C isotopic composition
tury, Japanese food has become popular in Brazil. Today, there are (express as δ13C) is distinct between these two types of plants (Farquhar
more than 700 Japanese restaurants in the city of São Paulo alone, and et al., 1989). Consequently, δ13C has been widely used to distinguish
more than 3000 nationwide (ABRESI Gastronomia, Hospedagem e the botanical origin of carbon in several types of foods (e.g. Camin
Turismo, 2015). et al., 2017). The C4 plants are widely present in the Brazilian food
Soy sauce (known as shoyu in Japan and Brazil) is one of the key system (Martinelli et al., 2011; Chalk, 2016), since Brazil is one of the
condiments in Asiatic countries. Traditionally, there are two kinds of largest producers of maize, sugarcane and free-range cattle, fed by C4
soy sauce: fermented soy sauce, made with prolonged fermentation African grasses of the genus Brachiaria.
processes by microorganisms, and chemical soy sauce, made through The price of maize in Brazil has been approximately half of the price
hydrolysis of vegetable protein (Nunomura and Sasaki, 1992). The Ja- of soybean in the last decade (CEPEA, 2017). This fact coupled with
panese-type soy sauce is traditionally produced by fermentation of legislation that allows the use of maize to produce shoyu, may tempt
soybeans and wheat (Steinhaus and Schieberle, 2007). In the Chinese- Brazilian producers to use a large amount of this cereal instead of
type, wheat is not included in the fermentation process (Nunomura and soybean to produce shoyu. Based on this fact, the main objective of this
Sasaki, 1992), whereas Korean soy sauce is produced with soybeans and paper is to use the stable carbon isotopic composition of shoyu made in
barley meal (Steinhaus and Schieberle, 2007). Additives, such as sugars, Brazil to estimate the relative contribution of C3 (probably soybeans)
caramel, monosodium glutamate, acidulants, and citric acid, could also and C4 (probably maize) to this condiment. As shoyu is widely known to
be included in soy sauce (Jakobi et al., 2017). be a soy-based sauce, our null hypothesis is that the main botanical
Shoyu is now the second most popular sauce-based condiment made component of this condiment will be soybeans, which is a C3 plant.
in Brazil after ketchup. Last year, more than 30,000 tons of shoyu were Accordingly, we expect shoyu to have δ13C < −25‰. We also
⁎
Corresponding author.
E-mail address: maristelacm@usp.br (M.C. Morais).
https://doi.org/10.1016/j.jfca.2018.04.001
Received 17 January 2018; Received in revised form 26 March 2018; Accepted 2 April 2018
Available online 03 April 2018
0889-1575/ © 2018 Elsevier Inc. All rights reserved.
M.C. Morais et al. Journal of Food Composition and Analysis 70 (2018) 18–21
where Rsample and Rstd are the 13C/12C or 15N/14N ratios of the sample
and standard, respectively (Pee Dee Belemnite limestone). The analy-
tical error was 0.2‰ for δ13C, and 0.3‰ for δ15N.
To estimate the relative contribution of C3 plant (probably soybean)
and C4 plant (probably maize), we used a simple isotopic dilution Fig. 1. Histogram of δ13C (A) and δ15N (B) of Brazilian shoyus.
model (Eq. (2)), where:
contribution estimated by Eq. (2). For instance, if Eq. (2) resulted in a
δ − δc 4 ⎞
C3 (%) = 100 × ⎛ C3 ⎜ ⎟ C3 contribution of 50%, the error associated with this value would be
⎝ δC 4 − δC 4 ⎠ (2) 50% ×0.06 = 3%.
Where, C3 (%) is the relative contribution of C3 plants, expressed as
percentage, δshoyu is the carbon isotopic composition of shoyu sample; 3. Results
and δC3 and δC4 is the carbon isotopic composition of putative raw
materials. Although wheat, rice, barley and other cereals could be used The average ( ± standard deviation) δ13C of the Brazilian shoyu was
in shoyu, soybean is the main raw material. Therefore, we assume the −15.0 ± 3.4‰, with a minimum δ13C of −27.6‰ and a maximum of
average stable isotopic composition of ten samples of soybeans acquired −12.1‰. The histogram of δ13C shows a skewed distribution with most
in the local market (−25.7 ± 1.3‰) as the δC3. Using the same ra- values varying between −14‰ and −12‰ (Fig. 1A). On the other
tionale, we assumed that in Brazil the main source of C4 plants is the hand, the δ13C values of shoyu from other countries were very distinct
fermentation of maize, although molasses and caramel could be used as compared to the Brazilian ones. For instance, the average ( ± standard
additives to shoyu. Accordingly, the δC4 was assumed to be the average deviation) δ13C of five shoyu samples from Japan was −25.2 ± 0.6‰.
δ13C value of fifteen maize samples also acquired in the local market The δ13C of shoyu samples from US (−25.3‰) and Singapore
(−11.4 ± 0.4‰). (−25.9‰) were close to Japanese samples. The δ13C values of Shoyu
We estimated the error associated with the isotopic dilution model from China (−20‰ and −15.4‰) and Taiwan (−20.2‰) were higher
as: than those from Japan, Singapore and US but still lower than the δ13C
2 2 of Brazilian samples (Table 1).
⎛ stdmaize ⎞ ⎛ stdsoy ⎞ There was a large variability of δ15N in Brazilian shoyu samples,
Error (%) = 100x ⎜ avg + 100x ⎜
maize ⎟ avgsoy ⎟ from −5‰ to 4‰, however, most of the values varied from −1‰ to
⎝ ⎠ ⎝ ⎠ (3)
2‰, and the average value was 0.3 ± 1.2‰ (Fig. 1B). The variability
Where, stdmaize and stdsoy are the standard deviations of maize (0.4‰) in the samples from other countries was much lower, from 1.1‰ to
and soy (1.3‰) endmembers, respectively; and avgmaize and avgsoy are 1.8‰, and the average was 1.4 ± 0.3‰ (Table 1).
the average values of maize (11.4‰) and soybean (−25.7‰), respec- A plot of δ13C vs. δ15N shows the distribution of Brazilian shoyu
tively. Using Eq. (3) the estimated error was equal to 6% of the relative samples compared with the average isotopic values of maize, and
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M.C. Morais et al. Journal of Food Composition and Analysis 70 (2018) 18–21
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M.C. Morais et al. Journal of Food Composition and Analysis 70 (2018) 18–21
Funding
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
Acknowledgments
Fig. 3. Price of soybean and maize per tonne in Brazil from 2007 to 2017 (from References
CEPEA (2017)).
ABRESI Gastronomia, Hospedagem e Turismo, 2015. Francal cria feira para impulsionar
negócios, gastronomia e preservação da memória da culinária japonesa. Retrieved
amount of maize found in shoyu made in Brazil is a case of food adul- November 27, from: http://abresi.com.br/francal-cria-feira-para-impulsionar-
teration. On the other hand, on ethical grounds, it is hard to accept that negocios-gastronomia-e-preservacao-da-memoria-da-culinaria-japonesa.
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Although we analyzed few samples of shoyu from other countries, it BRAZIL, 2017. Ministry of Tourism. Retrieved June 16, 2017, from http://www.brasil.
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Chinese and one Taiwanese shoyu samples. Sugar is listed as an in- CEPEA, 2017. Retrieved December 17, 2017 from: https://www.cepea.esalq.usp.br.
Camin, F., Boner, M., Bontempo, L., Fauhl-Hassek, C., Kelly, S.D., Riedl, J., Rossmann, A.,
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that the added sugar was probably derived from sugar cane. However, in legal cases. Trends Food Sci. Technol. 61, 176–187.
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mated at only 20% (Table 1). In this case, it is difficult to believe that (9), 1039–1050.
only C4 sugar was added to this product and probably maize was also FAOSTAT, 2017. Retrieved December 17, 2017, from: www.faostat.fao.org.br.
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We believe that the lower cost of maize in comparison with soybean Figueira, A.M.S., Davidson, E.A., Nagy, R.C., Riskin, S.H., Martinelli, L.A., 2016.
is the main motivation for Brazilian shoyu producers to use maize in- Isotopically constrained soil carbon and nitrogen budges in a soybean field chron-
stead of soy. Fig. 3 shows that from 2007 to 2017, the average price of osequence in the Brazilian Amazon region. J. Geophys. Res.: Biogeosci. 121 (10),
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soy was twice that of maize. Therefore, the large use of maize would
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significantly decrease the production costs of shoyu in Brazil. gerprint of soy sauces via hydrophobic surface interaction. Food Chem. 218,
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Taiwan had a large proportion of C4 plants, too. These sauces are darker
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the Chinese shoyu samples that we studied had a δ13C of −15.4‰, low molecular weight fractions obtained from three types of Japanese soy sauce
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umami flavor, which is due to several different types of compounds
(Lioe et al., 2007, 2010; Kaneko et al., 2011; Kamal et al., 2016). The
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