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Food Research International 130 (2020) 108924

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Food Research International


journal homepage: www.elsevier.com/locate/foodres

Review

A paradigm of volatile aroma compounds in rice and their product with T


extraction and identification methods: A comprehensive review
Deepak Kumar Verma , Prem Prakash Srivastav

Agricultural and Food Engineering Department, Indian Institute of Technology Kharagpur, Kharagpur 721 302, West Bengal, India

ARTICLE INFO ABSTRACT

Keywords: The aroma in rice and its products is one of the important quality characteristics. It is contributed by more than
Rice aroma 500 different volatile compounds and the extraction and quantification of aroma compounds are equally es-
2-AP sential, determining the threshold of aroma. Till date, a complete review of the aromatic consideration of rice is
Simultaneous distillation and supercritical fluid lacking in the literature. Therefore, the present paper is prepared with the aim of summarizing the data and
extraction
other significant information in respect of the aroma characteristics of different types of rice and rice pro-
Solid-phase microextraction
ducts from the early 1980s to 2019. This review discusses all the studies on extraction, isolation, and char-
Gas chromatography-mass spectrometry
Gas chromatography-flame ionization detector acterization of volatile aroma compounds (VACs) done in different types of rice and their products which will
further help researchers to continue their work on the lacking aspects of rice aroma. A special focus has been
given to the 2-AP compound which signified the difference between aromatic and non-aromatic rice cultivars.

1. Introduction development and application of chromatography, especially gas chroma-


tography (GC) which was widely used. GC received tremendous advances
The staple food in several parts of the world, especially in Asia and and innovations and in particular, when combined with mass spectrometry
India is rice (Oryza sativa L.). In the world, there are several types of rice (MS) known as GC–MS, made much easier to the identification and
found which are used in the preparation of numerous products. Some of quantification of VACs in mixtures of the sample matrix and have greatly
them are known for their aroma, flavor, and fragrance, due to the pre- increased our knowledge on chemistry of rice aroma. From an appraisal of
sence of aroma, flavor, and fragrance, rice’s products are more preferred all known information shows that there were more than 500 volatile aroma
by majority of consumers. Aroma quality of rice is a key characteristic compounds (VACs) which have been documented so far in various cultivars
that increases the value of rice in the international market. The Indian of scented and non-scented rice (Verma & Srivastav, 2016, 2018a).
subcontinent is a home for aromatic rice diversity. Traditionally, many As a result, there are many studies have been focused on extraction,
cultivars of aromatic and non-aromatic rice are grown by Indian farmers identification, and quantification of the VACs of rice and rice products.
(Singh, Singh, & Khush, 2000; Verma, Mohan, Yadav, Asthir, & Soni, The aim of most of the studies was for much better understanding of all
2012; Verma, Mohan, & Asthir, 2013; Verma, Mohan, Prabhakar, & those compounds which responsible characteristic aroma
Srivastav, 2015; Verma, Srivastav, & Nadaf, 2018c). (Bhattacharjee, Singhal, & Kulkarni, 2002; Itani, Tamaki, Hayata,
Rice aroma – the vital quality parameter may determine the ac- Fushimi, & Hashizume, 2004; Nadaf, Krishnan, & Wakte, 2006; Singh
ceptance or rejection of rice before it is tasted. On the other hand, it is a et al., 2000). However, some research focussed on other aspects of rice
primary sensory quality characteristic for consumers, is composed of VACs like aroma synthesis and development, development of rapid
taste and odor. Consumers of traditional rice consider aroma as the extraction and identification methods, etc. The works of many re-
major criteria. It is conjointly thought of as a crucial property of rice searchers and research groups associated with rice VACs throughout the
that indicates the top quality and value within the market (Singh et al., different parts of the world were appreciable. Among them, the major
2000; Verma & Srivastav, 2018b). researchers and research groups are given as follow since its first report:
Early research on rice aroma can be traced 30 years back (Okpalaa, Buttery, Ling, and Juliano (1982, 1983a, 1983b, 1986, 1988, 1999),
Moa, Duana, & Tanga, 2019; Routray & Rayaguru, 2018; Verma & Widjaja, Craske, and Wootton (1996a), Widjaja, Craske, and Wootton
Srivastav, 2018b; Wakte et al., 2016), but more scientifically progress in (1996b), Bergman et al., 2000, 2001), Grimm, Champagne, Bett-
modern analytical techniques has been achieved since the discovery, Garber, and Ohtsubo (2000), Grimm, Bergman, Delgado, and Bryant


Corresponding author.
E-mail address: deepak.verma@agfe.iitkgp.ernet.in (D.K. Verma).

https://doi.org/10.1016/j.foodres.2019.108924
Received 29 September 2019; Received in revised form 11 December 2019; Accepted 15 December 2019
Available online 18 December 2019
0963-9969/ © 2019 Elsevier Ltd. All rights reserved.
D.K. Verma and P.P. Srivastav Food Research International 130 (2020) 108924

(2001), Grimm et al. (2011), Wongpornchai, Sriseadka, and phenols, pyrazines, pyridines, and other compounds. Including these,
Choonvisase (2003), Wongpornchai, Dumri, Jongkaewwattana, and Siri some other compounds are also but they are extracted by the break-
(2004), Bhattacharjee, Ranganathan, Singhal, and Kulkarni (2003), down chemicals like fatty acids (FAs) which are presented in samples
Champagne et al. (1997), Champagne et al. (2004), Champagne et al. (Bergman et al., 2000). The VACs released after cooking is different
(2005), Champagne (2008), Itani et al. (2004), Yoshihashi (2002), from those released in the field at flowering time.
Yoshihashi et al. (2004), Yoshihashi et al. (2005), Bryant, Jones, and The aroma is considered by rice consumers in India and the world as
Grimm (2006, 2011), Nadaf et al. (2006), Ghiasvand, Setkova, and the 3rd most desired characteristic taken after by taste and elongation
Pawliszyn (2007), Zeng, Zhang, Chen, Zhang, and Matsunaga (2008a), after cooking (Bhattacharjee et al., 2002; Verma & Srivastav, 2016,
Zeng, Zhang, Zhang, and Chen (2008b), Zeng, Zhang, Zhang, 2018b). In cooked rice, there are studied on several aroma attributes;
Tamogami, and Chen (2009), Maraval et al. (2008), Maraval et al. for instance, bland-like, bran-like, brown rice, burned-like, burnt-like,
(2010), Yang, Lee, Jeong, Kim, and Kays (2008a), Yang, Shewfelt, Lee, buttery-like, cold-steam-bread-like, corn-like, corn-leaf-like, cracker-
and Keys (2008b), Yang et al. (2010), Yang et al. (2012), Goufo et al. like, dusty-like, earthy-like, fermented-sour-like, floral-like, gasoline
(2010), Goufo et al. (2011), Mathure, Wakte, Jawali, and Nadaf (2011), aroma-like, grainy-like, hot-steam-bread-like, musty-like, nut-like,
Mathure, Jawali, Thengane, and Nadaf (2014), Poonlaphdecha et al. paint-like, pandan-like, pearl-barley, plastic-like, popcorn-like, potato-
(2012), Poonlaphdecha et al. (2016), Deng et al. (2013), Deng et al. like, rancid-like, raw-dough-like, rice milk-like, smoky-like, spicy-like,
(2016), Mo et al. (2015), Mo et al. (2016), Mo et al. (2018), Mo et al. sulfur-like, tortilla-like, vegetable-like and white glue-like (Verma &
(2017), Hinge, Patil, and Nadaf (2016a, b), Li et al. (2016), Li et al. Srivastav, 2018a). Popcorn aroma, which occasionally called as pandan
(2019), and Sansenya, Hua, and Chumanee (2018). (Pandanus amaryllifolius) like aroma, was contributed by 2-AP in rice.
The primary goals of the researchers and research groups were to The 2-AP is the most important and prominent aroma chemical since it
distinguish those compounds which were answerable for the char- was used to identify in rice cultivars (Petrov, Danzart, Giampaoli,
acteristic rice aroma. For rice aroma, there were many attempts made Faure, & Richard, 1996; Verma & Srivastav, 2018b). Yajima, Yani,
to search for the key compounds in past many years back to till the date, Nakmura, Sakakibara, and Hayashi (1979) identified α-pyrrolidone as
but could not reported any single compound or set of compounds which the main odorant in Kaorimai (O. sativa japonica) – an aromatic rice on
are answerable for the full rice aroma. Buttery et al. (1982) revealed the cooking during the study of VACs and also reported to the presence of
first VAC, 2-acetyl-1-pyrroline (2-AP) in 1982 while the same authors in indole. Buttery, Turnbaugh, and Ling (1988) identified seven com-
1983 discovered it in aromatic rice due to its impact volatile character. pounds viz. 2-AP, (E,E)-2,4-decadienal, (E)-2-decenal, (E)-2-nonenal,
After the recognition of 2-AP as a key aroma constituent in cooked rice, decanal, nonanal and octanal with low odor thresholds from listed 64
it is generally believed that the characteristics of various kinds of rice aroma volatile chemical compounds i.e. known in rice. Latter, the
consist of a balance of very complicated mixtures of volatile/aromatic chemical compound 2-AP was considered as the key odorant con-
compounds in the rice (Mahatheeranont, Keawsa-ard, & Dumri, 2001; tributor of volatiles to rice aroma had a scent like popcorn (Bao et al.,
Yang et al., 2008a; Park, Kim, & Baek, 2010; Wu, Shan, & Ren, 2011; 2018; Boontakham, Sookwong, Jongkaewwattana, Wangtueai, &
Deng et al., 2013; Fukuda, Takeda, & Yoshida, 2014; Lee, Oh, Kim, & Mahatheeranont, 2019; Lei et al., 2017; Li et al., 2019; Okpalaa et al.,
Cho, 2019). There are no single selected analytical techniques used for 2019; Routray & Rayaguru, 2018; Verma & Srivastav, 2018b; Wakte
the investigation of VACs from rice and rice’s products sample matrix. et al., 2016). However, aldehydes, phenols, and nitrogen (N2)- and
Although, presently numerous technological innovations are accessible sulfur (S)-based VACs were responsible for the flavor of aromatic rice
for extraction of rice VACs and also these innovations have been during cooking (Buttery et al., 1988; Jezussek, Juliano, & Schieberle,
changed time-to-time according to requirement and many are still being 2002). Although in rice, 2-AP odorant contributor of volatiles is found
in under process to emerge a new development, mainly the distillation at different concentrations (1–10 ppb to 2 ppm) (Routray & Rayaguru,
and extraction concept. 2018; Wakte et al., 2016). The study revealed that VACs, such as (E)-2-
Some studies discussed many cultivars of rice as a bland tasting food decenal, (E,E)-2,4-nonadienal, and (E,E)-2,4-decadienal obtained from
and reported that minor chemical alterations may turn the rice and its fragrant as well as non-fragrant rice, are the products of lipid oxidation
products into totally unacceptable food (Maga, 1984). This was the responsible for contributing their distinctive aroma to glutinous or
main driving force for flavor chemists to insight into the aroma science waxy rice (Grimm et al., 2000; Widjaja et al., 1996b).
of rice. This discussion on the aroma of rice began with a number of
significant further advances. Thus, this review paper is written with the 3. Classification and odor description of rice aromas
aim of collecting, analyzing and summarizing the data and other im-
portant information obtained from the studies of the early 1980s to 3.1. Classification of rice aromas
2019. All the information will be compiled in an easy way in this paper
for researchers and scientists which may not be readily available to The majority of rice VACs have popcorn-like smell due to 2-AP
them. content. Aroma similar to taste and elongation after cooking of rice is
The present review overviews the specific topics which highlight the considered as a desirable quality for consumer acceptability. Rice ar-
importance of rice aromas, their classification, and odor description, as omas were classified into five major groups as given in Table 1. Al-
well as different types of rice and their major products which are em- though, any single chemical compound is not responsible for any spe-
ployed for aroma study and VACs identified from these sample ma- cific aroma in cooked rice, a combination of compounds in the fix
trices, have been focused. In addition, traditional and recently used proportions is responsible for specific aromas in cooked rice. It has
methodologies for extraction, identification, and quantification of VACs shown very clear in Table 1. For instance, fresh green or woody smells
have also been discussed. were contributed mainly by aldehydes, ketones, and some alcohol;
fruity and floral smell is due to the presence of heptanone, ketones, and
2. Importance of rice aromas 6-methyl-5-hepten-2-one while benzaldehyde and 2-pentyfuran pro-
vided nutty aromas (Widjaja et al., 1996b).
The aroma in rice grains that is contributed by several different
VACs have been identified which are the result and synthesized from 3.2. Odor description of rice aromas
distinct biochemical pathways. Two hundred or more different rice
varieties are outreaching in which numerous VACs were recorded Odor does not receive more attention as compared with other sense
(Verma & Srivastav, 2018b). These VACs include a series of compounds organs. This is much undeserved as the odor is applied more than of our
like; aldehydes, ketones, organic acids, alcohols, esters, hydrocarbons, knowledge and understandings. For illustration, the taste of a product is

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D.K. Verma and P.P. Srivastav Food Research International 130 (2020) 108924

Table 1
Classification of rice VACs.
S. N. Type of Rice Aroma Responsible Chemical Compounds

1. Green Aldehydes, Some alcohol and Ketones, (E)-2,(E)-4-hexadienal, (E)-2-hexenal, (E)-2-octenal, (E)-3-octen-2-onea, 2-heptanone, 2-methyl-2-pentanol,
Benzaldehyde, Decanal, Geranyl acetone, Methyl heptanoate, and n-hexanal
2. Fruity/Floral (E)-2,(E)-4-hexadienal, (E)-3-octen-2-onea, 2-hexanone, 2-nonanone, 2-undecanone, 6-methyl-5-hepten-2-one, Heptanone, Ketones, Methyl
heptanoate, n-heptanal, n-nonanal and n-octanol
3. Roasty 2, 3-octanedione
4. Nutty (E,E)-2,4-nonadienal, 2-pentyfuran, 4-vinyl guaiacol, and Benzaldehyde
5. Bitter Benzaldehyde and Pyridine

Sources: Verma and Srivastav (2018a).

Table 2
Odour description of VACs of rice (cooked and uncooked, both).
VACs Odour Description VACs Odour Description

(E) −3-Octene-2-one Green and fruity-like 2-undecanone Fruity and floral-like


(E)-2, (E)-4-decadienal Fatty and waxy-like 3-Octen-2-one Citrus, floral, herbal
(E,Z)-2,4-decadienal Fatty, waxy and green-like 3-Ethyl-2,5-dimethylpyrazine Cooked rice, nutty
(E,E)-2,4-decadienal Chicken, fatty 4-vinyl-guaiacol Unpleasant, nutty, spicy and clove-like
(E)-2, (E)-4-heptadienal Fatty and hay-like 4-vinylphenol Unpleasant and Phenolic-like
(E,E)-3,5-octadien-2-one Fruity, green, medicinal 6-methyl-5-hepten-2-one Banana-like
3,5-Octadien-2-one Fruity 2-Ethyl-6-methylpyrazine Almond
(E,E)-2,4-heptadienal Citrus, fruity, green Acetophenone Sweet and floral-like
(E,Z)-2,4-heptadienal Citrus, grass Benzaldehyde, Nutty and bitter-like
(E)-2, (E)-4-hexadienal Green and floral-like Benzothiazole Slightly and sweet-like
(E)-2, (E)-C nonadienal Waxy-like Benzeneacetaldehyde Floral, herbal
(E,E)-2,4-nonadienal Fatty, waxy and nutty-like Benzyl alcohol Slightly and sweet-like
(E)-2-decenal Fatty and waxy-like Decanal Green, soapy, citrus, sweet, waxy and floral-like
(E)-2-heptenal Herbaceous-like Decanoic acid Fatty-like
(E)-2-hexenal Fresh, fruity, Green-like, sweet d-limonene Fresh and sweet-like
(E)-2-nonenal Fatty, tallow, beany, cucumber and woody-like Ethanol Sweet-like
(E)-2-octenal Green and fatty-like Furfural Cooked rice, nutty, roasted, sweet
(E)-2-undecenal Fatty and sweet-like Geranyl acetone Magnolia and green-like
(E,E)-farnesyl acetone Flower-like Heptanal Fresh, Fruity, fatty, grass and rancid-like
(Z)-2-octen-1-ol Fatty-like Hexanoic acid Sweet and cheesy-like
1-heptanol Green and fruity-like Hexanol Herbaceous-like
1-hexanol Herbaceous-like Hexyl hexanoate Peach-like
1-nonanol Floral and citrus-like Indole Sweet, burnt, floral and mothball-like
1-octanol Citrus, fruity and floral-like l-pentanol Fusel oil-like
l-octen-3-o1 Raw mushroom-like Methyl heptanoate Green and fruity-like
2, 3-octanedione Roasted nuts-like Methylpyrazine Cooked rice, nutty, roasted
2-AP Sweet and pleasant, popcorn-like Naphthalene Naphthalene-like
2-decanone Fruity and orange-like n-heptanol Woody and sweet-like
2-Ethylhexenal Beany n-hexanal Green tomato, green and grass-like
2-decen-1-ol Citrus and rose-like n-hexanol Herbaceous-like
2-heptanone Fruity and floral-like n-octanol Fruity and floral-like
2-hexanone Fruity-like Nonanal Cucumber, floral, fruity, fresh, grass soapy and citrus-like
2-Ethylbenzaldehyde Nutty, roasted Nonanoic acid Fatty-like
2-methoxy-4-vinylphenol Spicy and clove-like n-pentanol Fuel oil-like
2-Methyl-2-pentenal Cooked rice, fruity, roasted, sweet Octanal Citrus, floral, green and slightly fruity-like
2-methoxy-phenol Smoky-like Octanoic acid Sweet and cheesy-like
2-n-Butylfuran Nutty, roasted Pentanal Woody and fruity-like
2-nonanone Fruity and herbaceous-like Pentyl hexanoate Fruity-like
3-Nonanone Caramel, spicy, sweet Phenol Medicinal and phenolic-like
2-ocetenal (E) Nutty, green, and fatty-like Phenylacetaldehyde Sweet (dilute) –like
2-octanone Fruity and floral-like Pyridine Pungent-like
2-pentylfuran Almond, beany, Floral, fruity, nutty, green and beany-like Dimethyl sulfide Sulfury
2-phenylethanol Sweet and floral-like Toluene Ethereal-like
2, 5-Dimethylpyrazine Nutty, roasted Undecanal Fresh and lemon-like
2, 3-Dimethylpyrazine Almond, nutty Vanillin Vanilla-like
2-tridecanone Oily and nutty-like γ-nonalactone Sweet and coconut-like

Source: Modified from Weber et al. (2000); Lam and Proctor (2003); Mottram (2007); Yang et al. (2008a); Yang et al. (2008b); Zeng et al. (2008a), Zeng et al.
(2008b); Zeng et al. (2009; Tananuwong and Lertsiri (2010); Khorheh et al. (2011); Bryant and McClung (2011); and Cho and Kays (2013)

determined by its odor for 90%. Our tongue is the only sense organs Most VACs noted so far from cooked aromatic and non-aromatic rice
among all parts of the body that has an ability to taste acids, acrid, salts, are the same except for their relative proportion. Even, researchers
and sweets. Unknowingly odor plays an important part in perception. reported 2-AP in both types of rice varieties/cultivars. Generally, rice is
Rice odor is an important factor for quality and consumer satisfaction. consumed as it's cooked form, so its VACs are of the great interest have
Probably, pleasant aroma of rice is due to the blend of chemical VACs among consumers but aromatic rice cultivars/varieties are an exception
(over 500) including aldehydes, ketones, organic acids, alcohols, esters, because its pleasant and sweet popcorn-like aroma is not only related
hydrocarbons, phenols, pyrazines, pyridines, and other compounds have with cooked rice. Although, in a cultivated field of these cultivars/
been reported in rice that describes to the odor description (Table 2). varieties quite often emit aroma during flowering time. For rapid

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D.K. Verma and P.P. Srivastav Food Research International 130 (2020) 108924

identification of aromatic rice varieties in the field, generally done by compound which is found commonly in plenty of conventional rice
chewing of immature grains is one among the methods quite often used cultivars, including glutinous, black, scented, and non-scented (2008b;
(Mittal, Preet, Singh, Shukla, & Saini, 1995). Yang et al., 2008a; Zeng et al., 2009) wherein it provides ‘almond’ and
Whether VACs are released in the field during the flowering time ‘nutty’ like odor. A strong characteristic of nutty and bitter-like aroma
which far differs from those VACs released after cooking of the rice is an exhibited by benzaldehyde and 2-pentylfuran, were also identified
important question to be answered. Of particular significance, these (Zeng et al., 2008a, 2008b). 1-octen-3-ol was identified to have raw
VACs are the particular factor that is very essential for quality of cooked mushroom-like marked odor (Kaiser, 2006) and reported in rice by
rice because aroma is fetched as the second utmost desired character- many workers (2008b; Bryant & McClung, 2011; Khorheh et al., 2011;
istic among the consumers next to the taste and elongation after Lam & Proctor, 2003; Tananuwong & Lertsiri, 2010; Weber et al., 2000;
cooking of rice. These VACs are representative of their different che- Yang et al., 2008a; Zeng et al., 2008a, 2008b, 2009). The compound viz.
mical class according to their significance as possible impact aroma alka-2, alk-2-enals, 2-pentylfuran, and 4-dienals were the most im-
compounds (Table 2) which have been described previously as odor- portant among VACs listed by Widjaja et al. (1996a) thus accounting to
active compounds (OACs) for description in cultivars/varieties of rice the rice aroma profile.
like cooked white or black rice of several japonica and indica cultivars
(2008b; Yang et al., 2008a) and/or flavour molecular markers used to 4. Aroma in different types of rice
distinguish three cultivars of Japanese rice (Zeng et al., 2008a). Other
studies have indicated that the distinctive aroma of cooked rice consists Globally, several types of rice are found and cultivated which differ
of a cross-section of important OACs and can't be satisfactorily char- from each other by the means of their wide range of specifications.
acterized by considering solely 2-AP concentration (2008b; Yang et al., These specifications include physical characteristics, milling char-
2008a). acteristics, chemical characteristics, and cooking and thermal char-
2-AP is being the major volatile in fragrant rice which can be used to acteristics. Some of them are described as:
distinguish between aromatic and non-aromatic rice. The nitrogen
carrying volatile compound indole, even at lower concentrations pos- 4.1. Rice wild type
sesses a floral or fruity and herbaceous fragrance (Kaiser, 2006). 2-AP
and indole, both VACs were selected as the indices of rice aroma Rice wild type is distinct type of annual grasses of the genus Zizania.
(Grimm, Lloyd, Godshall, & Braggins, 2004). They are also known by different names as Indian rice, Canada rice as
γ-Nonalactone possesses the coconut-like and sweet fragrance while well as water oats. Wild rice (Zizania aquatics) is one of four species
other lactones may provide aroma to rice bran and other food products grown in the United States and Canada. Other species have been
like rice cakes, fruits, wines, or liquors (Buttery, Orts, Takeoka, & Nam, identified in North America (Z. palustris and Z. texana) and in
1999; Fan & Qian, 2006; Fujimaki, Tsugita, & Kurata, 1977; Tsugita, Manchuria and the Far East (Oelke & Boedicker, 2000; Zhai, Lu, Zhang,
Kurata, & Fujimaki, 1978; Zeng et al., 2008a, 2008b; Zeng et al., 2009). Sun, & Lorenz, 2001). This type of rice is very distinctive in that the
On the other side, rice during storage may get rancid and generate grain is harvested under the moist conditions by American Indians for
oxidative off-flavors which are identified by the higher concentration of centuries as a staple of their diets and the kept for fermentation thus
hexanal (Bergman et al., 2000; Wongpornchai et al., 2004). leading to biochemical and microbiological changes finally resulting in
In the early stages of the aroma study, the following four com- a dark-colored product having distinct aroma, described as earthy,
pounds were considered to be important VACs of rice: 4-vinylphenol, grainy, nutty, toasted, roasted or tea-like (Withycombe, Lindsay, &
(E)-2-nonenal, (E,E)-2,4-decadienal and 2-methoxy-4-vinylphenol Stuiber, 1978).
(Buttery et al., 1988). (E)-2-nonenal is considered to produce a fatty, These rices are gaining popularity among consumers and have been
tallow, beany, cucumber and woody-like aroma (2008b; Bryant & commercially marketed to meet the increasing consumer’s demands due
McClung, 2011; Khorheh, Givianrad, Ardebili, & Larijani, 2011; Lam & to its unique flavors (nutty), texture, and nutritional benefits (Cho &
Proctor, 2003; Tananuwong & Lertsiri, 2010; Yang et al., 2008a; Zeng Kays, 2013). Studies report that wild rice is high in starch, protein,
et al., 2008a, 2008b, 2009) while (E,E)-2,4-decadienal possesses a fatty dietary fiber, minerals, and vitamins but it is low in fat. Wild rice is
and waxy-like odor (Weber, Rochelle, & Singh, 2000; Zeng et al., gluten-free (Gallaher & Bunzel, 2012) and is suitable for human con-
2008a, 2008b, 2009). Two VACs of them viz. (E,E)-2,4-decadienal and sumption. Most importantly, wild rice is investigated to be a good
(E)-2-nonenal were evaluated against other VACs & and reported as source of essential FAs such as linoleic and α-linolenic acid, antioxidant
important odorants for rice flavor (Zeng et al., 2008a). However, the phytochemicals especially ferulic, p-coumaric and vanilic acids, as well
VACs viz. 2-methoxy-4-vinylphenol, (E,E)-2,4-decadienal, and vanillin as nutraceuticals like γ-oryzanol (Przybylski, Klensprof-Pawlik, &
were confirmed as the most important odorants in four brown rice Anwar, 2009; Qiu, Liu, & Beta, 2009).
cultivars in the previous study (Jezussek et al., 2002). Wild rice is usually found in grocery and specialty stores where it is
4-vinyl guaiacol is another VAC of rice that has contributed off- sold either as dried grain or blended with other grains like O. sativa. It is
flavor in many of the food and food products viz. beer, apple juice, also incorporated in a variety of gourmet foods like breakfast cereals,
orange juice, and wort. This compound is one of the impact aroma desserts, soups, and meat dishes and available in that form also (Oelke
characters of cooked flavors and Maillard-type systems (McGorrin, & Boedicker, 2000; Qiu et al., 2009; Zhai et al., 2001). The grains of
2002). This VAC is a guaiacol derivative that has an unpleasant, nutty, wild type rice have achieved wide recognition since the 1950s for its
spicy and clove-like odor description in rice (2008b; Lam & Proctor, distinctive flavor by the gourmet food market. Recently, these rices
2003; Tananuwong & Lertsiri, 2010; Weber et al., 2000; Yang et al., have been increasingly used in rice mixes and casserole items which
2008a), and has been reported as an OAC in the cooked aroma of hulled feature wild rice as an ingredient since its first report in the literature
and milled rice of scented and non-scented cultivars (Jezussek et al., (Lund, Lindsay, Marth, & Stuiber, 1977; Withycombe et al., 1978). The
2002; Maraval et al., 2008). While this compound was identified by essential steps during the processing of wild rice are fermentation and
another researchers as a unique odorant in black rice (Yang et al., parching for developing the distinct flavor. Rice inoculated with -
2008a). In rice aroma, the undesirable changes may be caused by the Streptomyces spp. in a circulating nutrient medium to produce an
structural breakdown and migratory loss of aroma-active compound “earthy” flavor was rapidly spoiled by microorganisms indigenous to
(AAC) and/or formation of off-flavors associated with volatile products rice. Cultures of Pseudomonas perolens and P. taetrolens inoculated into
of lipid oxidation (Widjaja et al., 1996b). rice stored at 5 °C gave only mild methoxylated-pyrazine (green-earthy)
Benzaldehyde has been found as a vital aroma for wild rice (Cho & flavors to resulting processed rice (Mellinger, Marth, Lindsay, & Lund,
Kays, 2013). This is the 5th most important and abundant aroma 1982).

4
Table 3
Summary of some studies on VACs of different type of rice and their product.
Substrate Isolation and Extraction Identification and Quantification Number of Total Major/New Compound References
Method Method Identified
Compound

Black rice Sintoheugmi HsSPME GC–MS 54 2,5-dimethylnonane, 2-methylundecane, 4- (Choi et al., 2019)
propylbenzaldehyde, 5-methyldecane, methyl 2-
D.K. Verma and P.P. Srivastav

hydroxybenzoate, and methyl 2-methylpentanoate


Gluten-free Crumb and crust powders and rice flour SynDE GC-O 54 2-butyl-2-heptenal, 2-propyl-2-octenal, 4-hydroxy-2- (Boeswetter, Scherf, Schieberle, &
nonenoic acid lactone, 4-hydroxy-2-octenoic acid Koehler, 2019)
lactone, and 4-methylquinazoline
Meixiangzhan2 SynDE GC–MS – 2-AP (Li et al., 2019)
Thai fragrant rice cultivars, KDML 105 and PTT 1 SPME GC–MS – 2-AP (Boontakham et al., 2019)
‘Yungengyou 14′, Aromatic rice japonica type SynDE GC–MS – 2-AP (Mo et al., 2018)
Five hundred and fifty‐six rice genotypes (552 aromatic SvE GC–MS – 2-AP (Peddamma et al., 2018)
and four non-aromatic)
Meixiangzhan2 and Xiangyaxiangzhan fragrant rice SynDE GC–MS – 2-AP (Bao et al., 2018)
cultivars
Rice variety ‘Cheonjihyang-1-se’ HsSPME GC–MS 43 2-AP, dodecane, nonanal, octan-1-ol and tetradecane (Mahmud, Oh, Kim, Cho, & Lee,
2018)
Twenty-four different commercial white rice samples SPME GC–MS – – (Lim et al., 2018)
(12 from Korea and 12 from China)
Milled rice flour samples of nine Cambodian rice HsE Two-dimensional 231 – (Concepcion et al., 2018)
varieties GC × GC-time-of-flight-MS
Two rice cultivar: Apo and IR64 HsSPME GC–MS – – (Calingacion et al., 2017)
Aromatic rice cultivars, Yuxiangyouzhan and Nongxiang SynDE GC–MS – 2-AP (Mo et al., 2017)
18
Xiangyaxiangzhan and Guixiangzhan rice cultivars SynDE GC–MS – 2-AP (Lei et al., 2017)

5
Basmati-370, Ambemohar-157 (non-basmati scented), HsSPME GC–MS 54, 51, 39, – (Hinge et al., 2016b)
and IR-64 (non-scented) rice cultivars respectively
‘Basmati 385′ and ‘Nongxiang 18′ cultivars of aromatic SynDE GC–MS – 2-AP (Deng et al., 2016)
rice
Pare Wangi HsSPME GC–MS – 2-AP Adwita Arsa, Ariffin, and Aini
(2016)
Rice callus culture SPME GC–MS – 2-AP (Poonlaphdecha et al., 2016)
Scented rice cultivars Ambemohar-157 (AM-157) and HsSPME GC–MS 88 – (Hinge et al., 2016a)
Basmati-370 (BA-370) and non-scented rice cultivar
IR-64
Thirty one rice varieties HsSPME GC–MS – – (Mumm, Hageman, & Calingacion,
2016)
Two aromatic rice cultivars: Meixiangzhan and SynDE GC–MS – 2-AP (Li et al., 2016)
Nongxiang 18
Aromatic rice cultivars, Yuxiangyouzhan and Nongxiang SDCE GC–MS – 2-AP (Mo et al., 2015)
18
Four non-aromatic cultivars (Carnaroli, Carnise, Cerere, SPME GC–MS 25 1-octen-3-ol, 2-(E)-octenal, 2-AP, 2-methyl butanol, 2- (Griglione et al., 2015)
and Antares) and two aromatic (Apollo and Venere) pentyl furan, 3-methyl butanol, dec-(2E)-enal,
heptanal and octanal
Non-basmati scented indica rice varieties SPME GC–MS – 2-AP (Kaikavoosi et al., 2015)
Two rice cultivar: Apo and IR64 HsE GC-time-of-flight-MS 20 – (Calingacion et al., 2015)
Fragrant rice types (Jasmine, Basmati and Jasmati) SPME GC–MS, GC–O, and GC–PFPD 26, 23, and 22 2-acetyl-2-thiazoline, 2-AP, 2-methyl-3-furanthiol, 3- (Mahattanatawee & Rouseff, 2014)
respectively methyl-2-butene-1-thiol, α-ionone, β-damascenone, β-
damascone, dimethyl sulphide, dimethyl trisulfide,
geranyl acetate and methional
Ninety-one non-basmati scented rice cultivars HsSPME GC–MS 23 2-AP (Mathure et al., 2014)
Rice cultivars: Suwandal, Kuruluthuda, Kaluheenati, LNT and SvE GC-FID 14 1-pentanol, 2-AP, 2-butoxy ethanol, benzaldehyde, (Liyanaarachchi, Kottearachchi, &
Kuruluwee, Lanka-Samurdi, and non-fragrant rice benzyl alcohol, benzyl alcohol, hexanal, indole, Samarasekera, 2014)
variety Bg352 limonene, limonine, octanol and phenol
(continued on next page)
Food Research International 130 (2020) 108924
Table 3 (continued)

Substrate Isolation and Extraction Identification and Quantification Number of Total Major/New Compound References
Method Method Identified
Compound

Thirty-five rice samples HsE GC–MS 81 – (Fukuda et al., 2014)


Gbengbeng, Jebbehkomie, Buttercup, ‘Pla Camp, TTP GC–MS 33 (E,E)-2,4-heptadienal, 4-Ethylphenol, eucalyptol, (Cho, Nuijten, Shewfelt, & Kays,
Maalay’, Binta Sambou and ‘Painy Painy rice myrtenal, and pyridine, 2014)
D.K. Verma and P.P. Srivastav

cultivars
Two commercial rice varieties (Wuchang brand SPME GC–MS 77 – (Deng et al., 2013)
Japonica rice)
Wild rice cultivar “Minnesota” and brown rice TTP GC–MS and GC-O 71 and 33 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2-ethyl- (Cho & Kays, 2013)
respectively 6- methylpyrazine, 2-n-butylfuran, 2-pentylfuran, 3-
ethyl-2,5-dimethylpyrazine, benzaldehyde, and
furfural, methylpyrazine
Iranian fragrant rice (Hashemi, HD5, and HD6) HsSPME GC–MS 74, 55 and 66 56 including 2-AP (Givianrad, 2012)
respectively
Rice cultivar leaves and grains -Gladio × Fidji K2 SPME GC–MS – 2-AP (Poonlaphdecha et al., 2012)
Whole and ground rice HsE GC–MS – Hexanal (Wang & Ha, 2012)
Aromatic (Aromatic se2, Dellmati, Dellrose, IAC 600, SPME GC–MS 93 64 Bryant and McClung (2011)
Jasmine 85, JES, and Sierra) and non-aromatic
(Cocodrie and Wells) rice cultivars
Chinese rice cultivars, Zhengxian 8 (ZX), Nanjing 38 SPME GC–MS 40 (Wu et al., 2011)
(NJ), and Yannuo 12 (YN)
Fragrant rice cultivars (Guixiangzhan and SHsE GC-FID 12 2-AP (Goufo, Wongpornchai, & Tang,
Peizaruanxiang) 2011)
Iranian fragrant rice viz. Hashemi, HD5, and HD6 HsSPME GC–MS 75, 55 and 66 – (Khorheh et al., 2011)
respectively
Jasmine 85 SPME GC–MS – 2-AP (Bryant et al., 2011)

6
Jasmine rice and commercial rice brands SvE GC-FID – 2-AP (Grimm et al., 2011)
Mesona Blumes gum/rice extrudates LNT GC–MS 54 – (Fenga et al., 2011)
Pre-fluffed long grain rice (Sea Isle) SHsE GC-FID – 2-AP (Yahya et al., 2011)
Scented Rice HsSPME GC-FID – 2-AP (Mathure et al., 2011)
Aroma rice varieties SvE GC–MS – 2-AP (Ying et al., 2010)
Fragrant rice cultivars (Guixiangzhan and HsSPME GC–MS 42 – (Goufo et al., 2010)
Peizaruanxiang)
Fragrant rice cultivars (Guixiangzhan and SHsE GC-NPD – 2-AP (Goufo et al., 2010)
Peizaruanxiang)
Fragrant temperate japonicatype rice cultivars - SPME GC–MS – 2-AP (Gaya et al., 2010)
Aychade, Giano and Fidji
Korean non-aromatic rice DHsE and SDSvE GC–MS 10 and 16 2-MF and 2-AP (Park et al., 2010)
respectively
Organic red fragrant rice (Hom Daeng) SPME GC–MS 13 – (Tananuwong & Lertsiri, 2010)
Paddy rice SPME GC–MS 108 – (Lin et al., 2010)
Scented rice (Aychade, Fidji, Giano) and non-scented HsSPME Tandem GC–MS – 2-AP (Maraval et al., 2010)
cultivars (Ruille, Ariette)
Six premium-quality cultivars [Hwaseongbyeo (P1), DHsE with TTP GC-O 21 and 23 (E)-2-nonenal, 2-AP, guaiacol, heptanal, hexanal, and (Yang, Lee, & Kays, 2010)
Ilpumbyeo (P2), Gopumbyeo (P3), Taebongbyeo octanal
(P4), Chucheongbyeo (P5), and Samkwangbyeo
(P6)], two waxy cultivars [Hwaseonchalbyeo (W1)
and Hangangchalbyeo (W2)], and two black-
pigmented cultivars [Heugjinjubyeo (B1) and
Heugkwangbyeo (B2)]
Glutinous rice cultivars Modified HsSPME GC–MS 96 27 (Zeng et al., 2009)
Aromatic and non-aromatic rice DHsE with TTP GC–MS and GC-O 30 and 13 – Yang et al. (2008b)
respectively
Black and white glutinous SvE GC–MS 26 Benzaldehyde, 2-butanol, 1-propanol, 1,2- (Ajarayasiri & Chaiseri, 2008)
Rice (Kheow Ngu) propanediol, 1,2-propanediol, and 2,3-butanediol,
Food Research International 130 (2020) 108924

(continued on next page)


Table 3 (continued)

Substrate Isolation and Extraction Identification and Quantification Number of Total Major/New Compound References
Method Method Identified
Compound

Black glutinous rice SvE GC-FID – 2-AP (Bounphanousay et al., 2008)


Brown aroma rice SvE GC-FID – 2-AP Kim et al. (2008b)
Cooked black rice DHsE with TTP GC–MS and GC-O 35 and 25 2-AP and guaiacol (Yang et al., 2008a)
D.K. Verma and P.P. Srivastav

respectively
Japanese rice cultivars (Nihonbae, Koshihikari, and HsSPME GC–MS 46 – (Zeng et al., 2008a)
Akitakomachi)
Rice cultivar Tainung 67, SvE GC–MS – 2-AP (Huang et al., 2008)
Tainung 71 and 72
Rice cultivars with low-glutelin content (Shunyou, LGC- HsSPME GC–MS 77 (E,E)-2,4-decadienal, (E)-2-nonenal, 2-methoxy-4- (Zeng et al., 2008b)
katsu, and LGC-soft) vinylphenol, 2-pentylfuran, indole, and vanillin
Thirteen fragrant and six non-fragrant cultivars SvE GC–MS – 2-AP (Niu et al., 2008)
Thirteen specialty Korean rice samples TTP GC–MS and GC-O 19 (E,E)-2,4-decadienal, naphthalene, guaiacol, 2- (Limpawattana, Yang, Kays, &
heptanone, 2-AP, and (E)-2-hexenal Shewfelt, 2008)
Three scented cultivars (Aychade, Fidji, and Giano), SvE GC-O-FID and GC–MS 40 and 60 oct-1-en-3-one and 2-AP (Maraval et al., 2008)
non-scented cultivar (Ruille) and one scented respectively
commercial rice sample
Thai fragrant rice (Khao Dawk Mali 105) HsE GC-FID – 2-AP (Borompichaichartkul et al., 2007)
Iranian and Indian fragrant rice Cold fibre SPME GC-time-of-flight-MS – 2-AP (Ghiasvand et al., 2007)
Rice cultivar Aychade and commercially milled Basmati SPME GC–MS and GC-FID – 2-AP (Laguerre, Mestres, Davrieux,
rice Ringuet, & Boulanger, 2007)
Non-aromatic rice varieties, RD23, Supanburi 1 and SvE GC–MS – 2-AP, n-hexanal, (Laohakunjit & Kerdchoechuen,
Supanburi 90, and three aromatic varieties, KDML 2007)
and Pathumthani 1
Paddy rice SPME GC–MS 38 (E)-4-nonenal, hexadecanoic acid, ndecanal, n- (Zeng et al., 2007)

7
nonanal, and tetradecanoic acid
Aromatic rice cultivar, Kao Dawk Mali 105 (KDML 105) SvE GC–MS – 2-AP (Sirisoontaralak & Noomhorm,
2006)
Forty rice varieties SvE GC–MS with SIM – 2-AP (Hien, Yoshihashi, Sarhadi, &
Hirata, 2006)
Fragrant rice cv. Khao Dawk Mali 105 (KDML 105) MHsE SHs-GC-FID and SHs-GC-NPD – 2-AP (Sriseadka et al., 2006)
Premium rice (Koshihikari and Basmati) SPME GC–MS – Dodecanal and hexanal (Bryant et al., 2006)
Scented cultivated variety ‘Pusa’ basmati, non-scented SvE GC – 2-AP (Nadaf et al., 2006)
variety ‘Krishnahansa’ and marketed basmati rice
Aromatic variety, KDML 105 SvE GC–MS with SIM – 2-AP (Yoshihashi, Huong,
Surojanametakul, Tungtrakul, &
Varanyanond, 2005)
M−202 medium grain rice SPME GC–MS 14 2-heptanal, hexanal, I-pentanol, and nonanal (Champagne et al., 2005)
Thai fragrant rice LNT SDSvE GC–MS 94 2-AP (Sunthonvit et al., 2005)
Aromatic variety, KDML 105 SvE GC–MS with SIM – 2-AP (Yoshihashi, Nguyen, & Kabaki,
2004)
Commercial rice (Wells, Cocodrie, and Drew) SPME GC–MS 28 Hexanal, nonanal octanal, pentanal, pentanol, and (Monsoor & Proctor, 2004)
pentylfuran
Fortified Rice SPME GC–MS – – (Bett-Garber, Champagne, Ingram, &
Grimm, 2004)
Japanese aromatic rice: Hieri, Miyakaori and Sari Queen SvE GC–MS – 2-AP (Itani et al., 2004)
Rice cultivar Khao Dawk Mali 105 SvE and SPME GC–MS and GC-FID – 2-AP (Wongpornchai et al., 2004)
Rice cultivar: M−202 and Akitakomachi SPME GC–MS 10 – (Champagne et al., 2004)
Basmati rice of commercial brand LNT SDSvE and SCFs GC–MS 17 and 18 – (Bhattacharjee et al., 2003)
with CO2 respectively
Aromatic rice variety SvE GC–MS with SIM – 2-AP (Yoshihashi, Huong, & Inatomi,
(Khao Dawk Mali 105) 2002)
(continued on next page)
Food Research International 130 (2020) 108924
Table 3 (continued)

Substrate Isolation and Extraction Identification and Quantification Number of Total Major/New Compound References
Method Method Identified
Compound

Brown rice cultivars: Improved Malagkit SvAFEvE HR GC-O and HR GC–MS 41 (E,E)-deca-2,4-dienal, 2-amino acetophenone, 2-AP, 2- (Jezussek et al., 2002)
Sungsong, 370 Basmati and Khashkani methoxy-4-vinylphenol, 3-hydroxy-4,5-dimethyl-
2(5H)-furanone, 4,5-epoxy-(E)-dec-2-enal, bis-(2-
D.K. Verma and P.P. Srivastav

methyl-3-furyl)-disulfide, phenylacetic acid and


vanillin
Della and Dellmont HsSPME GC–MS – 2-AP (Bergman et al., 2001)
Jasmine rice SvE and SPME GC–MS – 2-AP (Grimm et al., 2001)
Khao Dawk Mali 105 brown rice Indirect SDE under Capillary GC–MS > 140 2-AP (Mahatheeranont et al., 2001)
reduced pressure and
controlled temperature
Della and Dellmont SvE GC-FID – 2-AP and hexanal (Bergman et al., 2000)
Basmati and Italian Line B5‐3 SDSvE GC and GC–MS 64 2-AP, 4-vinylguaiacol, benzaldehyde, hexanal, (Tava & Bocchi, 1999)
hexanol, indole, oct-1-en-3-ol, pentanal, and trans-2-
nonenal
Original, Brown, and white Paddy LNT SDE GC–MS 39 2-AP (Widjaja et al., 1996b)
Pelde, Basmati, Jasmine, Goolarah, YRF9 LNT SDE GC–MS 70 (E)-2,(E)-4-decadienal, (E)-2-octenal, (E)-Zheptenal, (Widjaja et al., 1996a)
2-AP, 2-pentylfuran, 2-phenylethanol, 4-
vinylguaiacol, 4-vinylphenol, alk-2-enals, alka-2,4-
dienals, alkanals, l-octen-3–01, n-hexanal, and n-
nonanal
Della, Basmati 370, and Jasmine SDSvE at low density HR GC–MS with SIM – 2-AP (Tanchotikul & Hsieh, 1991)
Louisiana Della rice and non-aromatic rice Lemont SDSvE GC–MS – 2-AP (Lin, Hsih, & Hoff, 1990)
Californialong-grain rice TTP GLC 64 (E)-2-nonenal, (E,E)-2,4-decadienal, 2-AP, 4- (Buttery et al., 1988)
vinylguaiacol, 4-vinylphenol, decanal, hexanal,

8
nonanal, and octanal
Milled rice SDCE Capillary GC–MS – 2-AP (Buttery et al., 1983b)
Wild Rice Vacuum SDSvE GC–MS 112 – (Withycombe et al., 1978)

Abbreviations: CO2: Carbon dioxide; DHsE: Dynamic headspace extraction; FID Flame ionization detector; GC: Gas chromatography; GC-O: Gas chromatography-olfactometry; GLC: Gas-liquid chromatography; HR: High
resolution; HsE: Headspace extraction; HsSPME: Headspace solid phase microextraction; LNT: Likens–Nickerson type; MHsE: Multiple Headspace Extraction; MS: Mass spectrometry; NPD: Nitrogen phosphorus detector;
PFPD: Pulsed flame photometric detector; SCFs: Supercritical fluids; SDCE: Steam distillation continuous extraction; SDE: Simultaneous/Steam distillation extraction; SDSvE: Simultaneous/Steam distillation and solvent
extraction; SHs: Static headspace; SHsE: Static headspace extraction; SIM: Selected ion monitoring; SPME: solid phase microextraction; SvAFEvE: Solvent-assisted flavour evaporation extraction; SvE: Solvent extraction;
SxLE: Soxhlet extraction; SynDE: Synchronization distillation and extraction; TTP: Tenax trap procedure.
- Not Reported.
Food Research International 130 (2020) 108924
D.K. Verma and P.P. Srivastav Food Research International 130 (2020) 108924

Table 4
Important world-wide scented rice varieties with grain-type and their geographical location of the origin and cultivation.
SRCs Grained type GLO&C SRCs Grained type GLO&C

A-301 cultivar (Jasmine-derived rice L-gT USA Kon Joha (1 and 2) S-gT India (Assam)
variety)
A-201 cultivar (Jasmine-derived rice L-gT USA Krishna Joha S-gT India (Assam)
variety)
Abdul M−gT India (Bihar) Kunkuni Joha S-gT India (Assam)
Achhu M−gT India (Himachal Pradesh) Kyeema** (Jasmine type rice L-gT Australia
variety)
Adamchini S-gT India (Uttar Pradesh) Lalmati** L-gT India (Uttar Pradesh)
Ahalami tarom** (Indica type traditional L-gT Iran Laloo L-gT India (Madhya Pradesh)
rice variety)
Ambemohar 102, 157 and 159 (Non- S-gT India (Maharashtra) Lam Thao** – Vietnam
basmati local type Indica rice variety)
Amod M−gT India (Bihar) Laungchoor S-gT India (Uttar Pradesh)
Amritsari S-&M−gT India (Andhra Pradesh) Lawangi** – Afghanistan
Anbarboo** (Indica type traditional rice M−gT Iran Lua Tam** (Traditional rice M−gT Vietnam
variety) variety)
Azucena (Japonica rice variety) L-gT Philippines Lua Thom** L-gT Vietnam
Badshah Pasand** S-gT India (Uttar Pradesh**, Bihar and Luke Qasan – Afghanistan
West Bengal,)
Badshahbhog* S-gT Bangladesh* and India (West Madhuri M−gT India (Madhya Pradesh)
Bengal, Orissa, Assam, Bihar and
Madhya Pradesh)
Bahami M−gT India (Bihar) Mahi Sugandha M−gT India
Bahantapul S-gT India (Uttar Pradesh) Malagkit Sungsong S-gT Philippines
Bahra* L-gT Afghanistan Malbhog S-gT India (Assam)
Baikani L-gT India (Bihar) Manikimadhuri Joha S-gT India (Assam)
Barangomati S-&M−gT India (Orissa) Mehr** – Iran
Basmati (Local) L-gT India (Rajasthan) Mentik Wangi – Indonesia
Basmati 50021–1 L-gT Pakistan Minghoutsiutsao – China
Basmati Pak L-gT Pakistan Mir tarom** (Indica type traditional L-gT Iran
rice variety)
Basmati* (Indica rice variety) L-gT India Mircha S-gT India (Bihar)
Basmati-185 L-gT Pakistan Mirza** – Iran
Basmati-370 L-gT India (Haryana, Punjab, Rajasthan Miyakaori* – Japan
and Uttar Pradesh) and Pakistan
Basmati-385 L-gT India (Punjab) and Pakistan Mohanbhog S-gT India (Bihar)
Basmati-386 L-gT India Monda Mashruqi – Afghanistan
Basmati-6129 L-gT Pakistan Moongphali S-gT India (Uttar Pradesh)
Basmati-D L-gT Bangladesh Mosa Tarom – Iran
Baspatri S-&M−gT India (Madhya Pradesh) Motachinaeum S-&M−gT India (Uttar Pradesh)
Basumati (Non-basmati local type Indica L-gT India Muskh Budgi S-gT India (Jammu and
rice variety) Kashmir)
Begmi M−gT India (Himachal Pradesh) Nagina 12 L-gT India (Uttar Pradesh)
Bengal Juhi S-gT India (Uttar Pradesh) Nahg Mort S4 – Thailand
Bengawan Solo* – Indonesia Nang Thom Cho Dao*,** L-gT Vietnam
(Traditional rice variety)
Bhabeli Joha S-gT India (Assam) Nang Thom Muon** (Traditional L-gT Vietnam
rice variety)
Bhantaphool S-gT India (Uttar Pradesh) Neda** (Indica type traditional rice L-gT Iran
variety)
Bhilahi Basmati M−gT India (Bihar) Nemat** Type (Indica type Long-grained Iran
traditional rice variety)
Bhugui S-gT India (Assam) Nep Bac** (Traditional rice variety) B-gT Vietnam
Bindli*** S-gT India (Uttar Pradesh Nep Hoa Vang*,** (Traditional rice B-gT Vietnam
variety)
Boga Joha S-gT India (Assam) Nep Rong** (Traditional rice B-gT Vietnam
variety)
Boga Tulsi S-gT India (Assam) Nizershail – Bangladesh
Bogamanikimadhuri S-gT India (Assam) Oitakoutou – Japan
Bogi Joha S-gT India (Assam) Pakistani Basmati L-gT India (Punjab and
Haryana)
Bokul Joha S-gT India (Assam) Panarsa local M−gT India (Himachal Pradesh)
Borjoha S-gT India (Assam) Pandanwangi – Indonesia
Borsal S-gT India (Assam) Pankhali-203 S-gT India (Gujarat)
BR-16** (Shahibalam) – Bangladesh Pare Kembang – Indonesia
BR-5** (Dolhabhog) – Bangladesh Parsam M−gT India (Uttar Pradesh)
Brahmabhusi S-gT India (Bihar) Pashadi – Afghanistan
BRRI Dhan-34*,** (Locally known as L-gT Bangladesh Pashadi Konar – Afghanistan
Khashkhani)
Chahao Amubi (black) M−gT India (Manipur) Permel – Afghanistan
Chahao Angangbi (pink/red) M−gT India (Manipur) Phu Xuyen – Vietnam
Champa* M−gT Iran Poya – Iran
Champaran Basmati (Bhuri, Kali and Lal) M−gT India (Bihar) Prabhavati M−gT India (Maharashtra)
Chatri M−gT India (Madhya Pradesh) Prasadbhog S-gT India (Assam)
(continued on next page)

9
D.K. Verma and P.P. Srivastav Food Research International 130 (2020) 108924

Table 4 (continued)

SRCs Grained type GLO&C SRCs Grained type GLO&C

Chenaur S-gT India (Bihar) Pulu mandoti – Indonesia


Cheniguti S-gT India (Assam) Punjab Basmati-l L-gT India
Chhoti Chinnawar S-gT India (Uttar Pradesh) Pusa Basmati-1** L-gT India
Chinigura* S-gT Bangladesh Qingbuxiangjingmi** – China
Chinisakkar S-gT India (West Bengal) Qufuxiangmi** – China
Chinni gauri S-&M−gT India (Madhya Pradesh) Radhuni Pagal – Bangladesh
Chinni sagar S-&M−gT India (Madhya Pradesh) Raibhog (Non-basmati local type – India
Indica rice variety)
Chinoor S-gT India (Maharashtra and Madhya Ram Tulsi S-gT India (Bihar)
Pradesh)
Chufon S-gT India (Assam) Rambhog S-gT India (Uttar Pradesh)
Congjiangxixiangmi** – China Ramjain S-gT India (Bihar)
Dadkhani** – Bangladesh Ramjawain S-gT India (Uttar Pradesh)
Danaguri S-gT India (West Bengal) Ramjinwain (T1) L-gT India (Uttar Pradesh)
De Chang Xiang Mi** – China Ramphal Joha S-gT India (Assam)
Dehradun or Amritsari Basmati L-gT India Ranbir Basmati** L-gT India
Dehraduni Basmati L-gT India (Uttar Pradesh) Randhunipagal S-gT India (West Bengal)
Della* (Jasmine-derived rice variety) L-gT USA Ranga Joha S-gT India (Assam)
Dellamont L-gT USA Rojo Lele – Indonesia
Deobhog S-gT India (Bihar) Royal L-gT India
Dewtabhog S-gT India (Bihar) Sabarmati L-gT India
Dhania S-gT India (Uttar Pradesh) Sadri*,** L-gT Iran
Di Huong** (Traditional rice variety) L-gT Vietnam Safeda L-gT India (Uttar Pradesh)
Domsiah** (Indica type traditional rice L-gT Iran Sagartara S-gT India (Orissa)
variety)
Dubraj L-gT India (Uttar Pradesh) Sakkarchinni S-&M−gT India (Uttar Pradesh)
Dubraj-354 S-gT India (Madhya Pradesh) Sakkorkhora M−gT Bangladesh
Duniapet (T9) L-gT India (Uttar Pradesh) Sakoli-7 M−gT India (Maharashtra)
Fajr** – Iran Salari** (Indica type traditional rice L-gT Iran
variety)
Gandheshwari S-gT India (West Bengal) Sang tarom** (Indica type L-gT Iran
traditional rice variety)
Gandhkasala S-gT India (Kerala) Sarda Bala – Afghanistan
Ganwanxian 22** – China Sari Queen – Japan
Gerdeh* S-&R-gT Iran Sasaminori – Japan
Ghansal** (Non-basmati local type Indica – India (Maharashtra) Sataria S-gT India (Bihar)
rice variety)
Goalporia Joha (1 and 2) S-gT India (Assam) Sawakaori – Japan
Goemjeongssal (Japonica black rice M−gT Korean Sela – Afghanistan
variety)
Golden Elephant* (Jasmine type indica L-gT Thailand Sela Doshi – Afghanistan
rice variety)
Gopalbhog M−gT India (Bihar) Sherkati – Afghanistan
Govindbhog S-gT India (Assam) Shiroudi – Iran
Hansraj L-gT India (Uttar Pradesh) Shuang-Zhu-Zhan** – China
Haryana Basmati-1** L-gT India Shyam Jeera S-gT India (Bihar)
Hassan Saraie** (Indica type traditional L-gT Iran Siamati* – Thailand
rice variety)
Hassani** (Indica type traditional rice L-gT Iran Sindigi Local S-gT Karnataka, India
variety)
Hawm Klong Luang** – Thailand Sintanur – Indonesia
Hawm Supanburi** – Thailand Sitabhog S-gT India (West Bengal)
Hieri** – Japan (Kochi) Situpatenggang – Indonesia
Huanglongxiangmi** – China Sona Lari S-gT India (Bihar)
Huyet Rong** L-gT Vietnam Sonachur M−gT India (Uttar Pradesh and
Bihar)
Hyangmibyeo 1 and 2 (Japonica rice M−gT Korean Sukhdas S-gT India (Andhra Pradesh)
variety)
Improved Basmati** L-gT India Super Basmati* (Premium variety L-gT Pakistan
of Pakistan)
Indrayani (Non-basmati local type Indica – India Surkha-Bala – Afghanistan
rice variety)
Izayoi – Japan Surkha-Daraz-Baghlan – Afghanistan
Jakou – Japan Surkhamabain – Afghanistan
Jakouine – Japan Suyunuo (Japonica rice variety) – China
Jasmine* (Jasmine type indica rice L-gT Thailand T (412 and 812) S-gT India (Orissa)
variety)
Jauphool S-gT India (Madhya Pradesh) T-9 L-gT India (Uttar Pradesh)
Jeerabattis S-gT India (Uttar Pradesh) Tainung Sen 20 – China
Jeeraga Samba M−gT India (Tamilnadu and Andhra Takhar – Afghanistan
Pradesh)
Jeerakasala S-gT India (Kerala) Takurabhoga S-gT India (Orissa)
Jiangyongxiangdao** – China Tam Canh** (Traditional rice L-gT Vietnam
variety)
Jiangyongxiangdao** – China Tam On** (Traditional rice variety) L-gT Vietnam
(continued on next page)

10
D.K. Verma and P.P. Srivastav Food Research International 130 (2020) 108924

Table 4 (continued)

SRCs Grained type GLO&C SRCs Grained type GLO&C

** *,**
Jingcixiangdao – China Tam Xoan (Traditional rice L-gT Vietnam
variety)
Jingxixiangdao** – China Ta-pei-mang – China
Joha Bora S-gT India (Assam) Tapovan Basmati L-gT India (Uttar Pradesh)
Kabashiko** – Japan Taraori Basmati L-gT India (Haryana)
Kagasali M−gT India (Karnataka and Maharashtra) Taraori Basmati** L-gT India
Kaki Rekhalu S-gT India (Andhra Pradesh) Tarom amiri** (Indica type L-gT Iran
traditional rice variety)
Kala Sukhdas L-gT India (Uttar Pradesh) Tarom deylamani** (Indica type L-gT Iran
traditional rice variety)
Kalanamak** M−gT India (Uttar Pradesh** and Bihar) Tarom mahalli** (Indica type L-gT Iran
traditional rice variety)
Kali Kamod S-&M−gT India (Madhya Pradesh) Tarom** (Indica type traditional L-gT Iran
rice variety)
*, ** *,**
Kalijeera S-gT Bangladesh and India (Assam) Tau Huong Lo** (Traditional rice L-gT Vietnam
variety)
Kalo Nunia S-gT India (West Bengal) Tau Huong Muon** (Traditional L-gT Vietnam
rice variety)
Kalu Mooch S-gT India (Madhya Pradesh) Tau Huong Som** (Traditional rice L-gT Vietnam
variety)
Kamina S-gT India (Bihar) Texmati* (A traditional American L-gT USA
white rice variety)
Kamini Joha S-gT India (Assam) Thai Hom Mali Rice – Thailand
Kamod (Non-basmati local type Indica – India Thakurbhog S-gT India (Uttar Pradesh)
rice variety)
Kamod-118 S-gT India (Gujarat) Tilak chandan** M−gT Uttar Pradesh**, India
Kanak Jeera S-gT India (Bihar and Uttar Pradesh) Tinsukhia S-gT India (Uttar Pradesh)
Kanakchur M−gT India (West Bengal) Torishi – Afghanistan
Kanakjeeri S-gT India (Bihar) Tulai Panji S-gT India (West Bengal)
Karia Kamod S-gT India (Bihar) Tulshimala – Bangladesh
Karmuhi M−gT India (Uttar Pradesh) Tulsi Manjari S-gT India (Bihar and Madhya
Pradesh)
Karnal local** L-gT India (Haryana) Tulsi Pasand S-gT India (Bihar)
Karpurkali S-gT India (Orissa) Tulsibhog S-gT India (West Bengal)
Kasmati* (Basmati type rice variety) L-gT USA Type 3 L-gT India (Uttar Pradesh)
Kasturi L-gT India Ukunamodhu – Bangladesh
Kataktara** – Bangladesh Vishnu Parag M−gT India (Uttar Pradesh and
Madhya Pradesh)
Katami S-gT India (Bihar) Vishnubhog S-gT India (Madhya Pradesh)
Katanbhog M−gT India (West Bengal) VRF6 – Australia
Kataribhog S-&M−gT India (Assam and West Bengal) Wuxiangjing** (Japonica rice – China
variety)
Kataribhog*, ** L-gT Bangladesh Xiang Keng 3** – China
KDML-105*, ** (Jasmine type indica rice L-gT Thailand Xiang Nuo 4** – China
variety)
Kesar M−gT India (Bihar and Uttar Pradesh) Xiangyou 63** – China
Khalsa 7 L-gT India (Haryana) Yongshunxiangdao** – China
Khao Hawm*,** (National pride of – Thailand Yuvraj S-gT India (Uttar Pradesh)
Thailand)
Khorika Joha S-gT India (Assam) Zeerasal S-gT India (Gujarat)
Kodus** – Ira Zhao Xing 17** – China
Kola Joha S-gT India (Assam) Zhe 9248** – China
Kolhapur Scented S-gT India (Gujarat)

Sources: Modified from Singh et al. (2000); Moulmein, Samadi, Wu, and Leung (2003); Shobha Rani, Pandey, Prasad, and Sudharshan (2006); Yang et al. (2012) and
Verma, Srivastav, and Nadaf (2018c)
Abbreviations: B-gT: Bold-grained type; L-gT: Long-grained type; M−gT: Medium-grained type; S-&M−gT: Short- and Medium-grained type; S-&R-gT: Short- and
round-grained type; S-gT: Small-grained type; GLO&C: Geographical Location of the Origin and Cultivation; SRCs: Scented Rice Cultivars; *Cultivar of Global Impact
and International Demand from respective geographical location of cultivation; **Popular land races from respective geographical location of cultivation; ***Far more
aromatic than popular varieties.

Literature concerned with the flavor chemistry of wild rice is non- discussed including 6 pyrazines. The widely present 6 compounds were:
existent. A handful of studies reported the chemical composition of wild benzaldehyde, 2,5-dimethylpyrazine, (E,E)-2,4-decadienal, hexanal,
rice aroma (Table 3) without any information and data about the (E,E)-2,4-heptadienal, and methylpyrazine; and other 67 aroma com-
consumer preference towards the cooked wild rice on the basis of pounds consisted of half of the total, nearly 49.8%. Approximately
aroma volatiles. A major study was first published on the isolation and 34.7% of total relative aroma concentration included the 12 pyrazines:
identification of VACs in relation to the product of wild rice grain using 2,3-dimethyl-5-ethylpyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyr-
vacuum steam distillation, and 112 compounds were found to con- azine, 2-ethyl-3,5-dimethylpyrazine, 2-ethyl-3-methylpyrazine, 2-ethyl-
tribute to the distinctive aroma of wild rice (Withycombe et al., 1978). 5-methylpyrazine, 2-ethyl-6-methylpyrazine, 2-isoamyl-6-methylpyr-
GC–MS identified the 71 VACs from cooked wild rice out of which the azine, 3-ethyl-2,5-dimethylpyrazine, ethenylpyrazine, ethylpyrazine
major groups were aldehydes (total 5 aromatic compounds out of 23) and methylpyrazine. The wild rice contains unique alkylpyrazines
and pyrazines (12 compounds). Earlier, 17 volatile compounds were which are not present in conventional black, brown, aromatic, and non-

11
D.K. Verma and P.P. Srivastav Food Research International 130 (2020) 108924

aromatic rice (2008b; Jezussek et al., 2002; Maraval et al., 2008; Yang Shida, 1977; Tsuzuki, Matsuki, Morinaga, & Shida, 1978; Tsuzuki,
et al., 2008a). Tanaka, & Shida, 1979; Tsuzuki, Machii, Shida, & Miura, 1979; Tsuzuki,
Likewise, GC-O detected the presence of 22 aroma compounds 1984; Tsuzuki, & Shimokawa, 1990). The summary of some studies on
which included the aldehydes (16 compounds), pyrazines (5 com- VACs of different scented type rice is stated in Table 3. The compound
pounds), ketones (4 compounds), and furans (3 compounds). The aroma 2-AP has been identified as a key aroma constituent contributing to
of wild rice was mainly attributed to benzaldehyde which was 5th most flavour of several scented rice varieties (Table 3). Nevertheless, two of
prevalent chemical compound, usually found in black, glutinous, aro- the most extensive studies were conducted on aromatic rice, one of
matic and non-aromatic rice (2008b; Yang et al., 2008a; Zeng et al., which recorded 114 compounds (Yajima et al., 1979), while the other
2009). Wild rice - popular for nutty aroma contained a higher amount documented more than 140 compounds (Mahatheeranont et al., 2001).
of 2-pentylfuran that contributed to the ‘beany’, ‘green’, and ‘almond’ On comparing the aroma of traditional rice with scented rice, earlier
aroma in conventional rice cultivars (Maga, 1979; Zeng et al., 2009). 2- ones contained the 1-hexanal, 1-hexanol, and 4-vinylphenol in higher
butylfuran was detected in glutinous rice from Japan which was how- concentration and contain indole in lower amount than scented rice
ever not related to aroma (Zeng et al., 2009). The food products usually (Yajima et al., 1979). Further, the scented rice also contained an uni-
contain ‘roasted’, ‘toasted’, and ‘nutty’ aroma due to the pyrazines (Ho dentified compound − 2-pyrrolidone, missing in regular rice (Buttery
& Riha, 1998) while in wild rice, the distinct aroma was carried due to et al., 1982, 1983b). In scented rice, 2-AP is considered as the major
the alkylpyrazines. The sensory panels recognized the moderate or VACs since the first report and also in recent research (Table 3),
higher odor intensities compounds – pyrazines contributing wild rice whereas firstly found in leaves of Pandanus species in 1 ppm reported
the ‘nutty’ aroma. The alkylpyrazines may be present in wild rice due to (Buttery, Juliano, & Ling, 1983a). It thus justified the culture of using
its unique processing conditions. 2-ethyl-6-methylpyrazine, among the pandan leaves during rice cooking to impart a scented aroma to rice.
five pyrazines was most potent aroma compound which deliver the The Pandanus leaves possess nearly 100 times higher concentration of
various aroma in different foods as identified in many studies such as: 2AP compared to regular rice varieties.
nutty and roasted odor in roasted hazelnut and buckwheat tea (Qin, Ma, Since at that point, few studies were attempted to know the dis-
Wu, Shan, & Ren, 2011), ‘fruity’ in roasted sesame (Schieberle, 1996) tinction in scented and non-scented rice on the premise of aroma vo-
and fruity/flowery aroma in coffee (Loapez-Galilea, Fournier, Cid, & latiles (Widjaja et al., 1996a). A detailed study has been found on vo-
Guichard, 2006). Panelists reported the 2-ethyl-6-methylpyrazine of- latiles that contribute to the rice aroma beyond 2-AP (Yang et al.,
fering ‘almond’ odor and pyrazines and furans contributing to ‘nutty’ 2008b). However, only a few studies were undertaken to quantify VACs
aroma in wild rice. Cho and Kays (2013) studied the impact VACs of Z. in non-basmati type local scented cultivars of Indian rice (Mathure
palustris and reported a total of 71 aroma compounds while OACs were et al., 2011; Nadaf et al., 2006). The floral, fruity or sweet aroma in rice
33 identified by using GC–MS, and GC–O, respectively. The dominant is mainly contributed by alcohols, amines, and phenols. A total of 19
aromas were noted as unique nutty and roasted types which were pri- alcohol derivatives were detected among which 5 are considered as
marily contributed by various VACs viz. furfural, 2,3-dimethylpyrazine, contaminants while 11 are present in aromatic and non-aromatic cul-
benzaldehyde, 2,5-dimethylpyrazine, methylpyrazine 3-ethyl-2,5-di- tivars thus showing their insignificance in differentiating the rice cul-
methylpyrazine, 2-ethyl-6-methylpyrazine, 2-pentylfuran, and 2-n-bu- tivars. The lipid degradation products such as aldehydes, alkanes, and
tylfuran. alkenes may be associated with the fatty, grassy, and soapy aroma
As discussed critically in the above section, only a few studies have which may either be pleasant or objectionable aroma based on the
been conducted on the flavor chemistry of wild rice. A total of 112 degree of these compounds. But usually, the rancid or off-flavor is re-
VACs are reported from the aroma profile of wild rice since the first lated to the higher level of lipid breakdown products. The hexanal is
study to till the date. However, advances in research on wild rice ar- used as an indicator of off-flavor in rice (Bergman et al., 2000;
omas continue but it is not possible at this point to conclude with the Wongpornchai et al., 2004). In scented rice cultivars, a huge number of
precision of wild rice aroma profiles because of (a) the lack of details on VACs (72–51) were identified during the growth phase compared with
the complete aroma profile of wild rice varieties, and (b) the lack of non-scented counterparts (Hinge, Patil, & Nadaf, 2016b). In addition to
data and knowledge on consumer preference for cooked wild rice based 2AP, there were several differences between the VACs of scented and
on volatile aromas. Hence, further research and investigations are re- non-scented rice (Bryant & McClung, 2011).
quired in this area.
4.3. Rice raw type
4.2. Rice scented type
Raw rice is considered to have a weak aroma which far differs from
Certain rice cultivars possess potent aroma compared to traditional the aroma of cooked rice. Raw rice has been considered for study to
ones and are known as scented rice which is also popular from other know and understand the VACs which were eagerly contributing to rice
names like “aromatic”, “pecan” or “popcorn” rice. Among these, aroma and it was noticed that the major contributor of aroma in raw
Basmati and Della are the two important major far-eastern and rice was played by hydrocarbons (Mahatheeranont et al., 2001). Sur-
American varieties, respectively popular in certain regions of the world. prisingly, little research works have been conducted to understand the
The majority of scented rice cultivars were short-grained, some are VACs of raw rice (Table 3). After harvesting when rice is stored above
medium-grained and only very few are long-grained (Table 4). These 1 year, it is known as “long-stored” or “old” rice and the resulting stale
varieties are highly thermos-photosensitive, long duration types and flavor is not considered as agreeable regardless of cooking. Several
low yielding performances. In scented rice, grain quality parameters scientists reported the hexanal, aldehydes, and some alcohols as the
were most important to the people who engaged with the production, dominant VACs while preserving the rice grains (Chikubu, 1970;
processing, and consumption of rice. The essential grain quality para- Legendre, Dupuy, Ory, & McIlrath, 1978; Shin, Yoon, Rhee, & Kwon,
meters in scented rice were hulling, milling, head rice recovery and 1986; Tsugita, Ohta, & Kato, 1983). However, the breaking-down me-
kernel length and width which is very useful for the flavor chemists and chanisms of hydroperoxides to hexanal remain ambiguous in rice
plant breeders in understanding the rice composition (Singh et al., grains. The prevalent isozyme component is LOX-3 in rice grain which
2000; Verma et al., 2012; Verma, Mohan, & Asthir, 2013; Verma, generates the 9-D-hydroperoxy-10,12(E,Z)-octadecadienoic acid (9-
Mohan, Prabhakar, & Srivastav, 2015; Verma, Srivastav, & Mohan, LOOH) from linoleic acid (Ida, Masaki, & Morita, 1983; Ohta, Ida,
2018b. Tsuzuki who authored a series of papers found the minor in- Mikami, & Morita, 1986; Yamamoto, Fujii, Yasumoto, & Mitsuda,
significant variation in aroma profile of scented and regular rice 1980). However, LOX-3 did not produce 13-L-hydroperoxy-9,11(Z,E)-
(Tsuzuki, Morinaga, Shida, & Danio, T. 1975; Tsuzuki, Morinaga, & octadecadienoic acid (13-LOOH) which is a hexanal precursor in higher

12
Table 5
Plants, animals and microbial sources in which 2-AP as major aroma contributor.
Sources of 2-AP Sample Type Extraction Methods Quantification Methods Concentration Level References

Plants: Sources of 2-AP


Almond (Prunus dulcis) Oil roasted type, SvED GC–MS 30 µg/kg (Erten & Cadwallader, 2017)
Dry roasted type SvED GC–MS 12 µg/kg
Baguette a French bread Crusts, a Intensifiee (INT) preparation SlED HR GC–MS 17 µg/L (Zehentbauer & Grosch, 1998)
D.K. Verma and P.P. Srivastav

preparation of wheat flours Artisanale (ART) preparation SlED HR GC–MS 11 µg/L


Bread flowers (Vallaris glabra) Dry flowers SDE GC–MS 26.12 ppm (Wongpornchai et al., 2003)
Fresh flowers SDE GC–MS 3.36 ppm
Fresh leaves SDE GC–MS 0.53 ppm
Coconut (Cocos nucifera L.) Aromatic type Acidic SvE followed by GC–MS and NPD 3.29–21.98 ppm (Saensuk et al., 2016)
transferring into Organic SvE
Coconut (Cocos nucifera L.) Nam-Homcultivar HsSPME GC–MS 0.6–7.5 μg/L (Luckanatinvong, Mahatheeranont, &
Siriphanich, 2018)
Liquid endosperm Acidic SvE followed by GC–MS 6.30 ppm (Dumhai et al., 2019)
Organic SvE
Young tender endosperm Acidic SvE followed by GC–MS 6.78 ppm
Organic SvE
Green tea Pan-fired type SDE GC–MS – (Kumazawa & Masuda, 2002)
Hazelnuts (Corylus avellana) Processed seed oils HVDE HR GC-O and HR GC–MS – (Matsui, Guth, & Grosch, 1998)
Honey [Linden (Tilia tomentosa)] Raw type SDE GC–MS 0.02–0.04 ng/l (Blank & Fischer, 1989)
Honey [Manuka (Leptospermum Raw type L-LE GC–MS 80–450 µg/kg (Ruckriemen, Schwarzenbolz, Adam, & Henle,
scoparium)] 2015)
Mahua (Bassia latifolia) Fresh flowers HsSPME GC–MS 3.30 ppm (Wakte, Kad, Zanan, & Nadaf, 2011)
Maize (Zea mays) Extruded flour – GC-O Traces (Bredie, Mottram, & Guy, 1998)
Mung bean (Vigna radiata) Seeds SDE GC–MS – Brahmachary and Ghosh (2002)
Seeds HsSPME GC–MS 0.19 ppm (Attar, Hinge, Zanan, Adhav, & Nadaf, 2017)

13
Seeds HsSPME GC–MS 0.19 ppm (Attar, 2014)
Leaves HsSPME GC–MS 0.119 ppm
Palm wine (Elaeis guineensis) Bottled packaged HVDE HR GC–MS 11.4 µg/kg (Lasekan, Buettner, & Christlbauer, 2007)
Pandan (P amaryllifolius) Freeze dried leaves SDE GC–MS 1.00 ppm (Buttery et al., 1983a)
Fresh leaves DSvE GC–MS 14.10 ppm (Thimmaraju, Bhagyalakshmi, Narayan,
Venkatachalam, & Ravishankar, 2005)
Fresh leaves HsSPME GC-FID 6.85 ppm (Wakte, Thengane, Jawali, & Nadaf, 2010)
Fresh leaves HsSPME GC-FID 0.09–4.98 ppm (Wakte, 2010)
Fresh leaves LNEA RDA and HP TLC 0.982 ppm (Bhattacharjee, Kshirsagar, & Singhal, 2005)
Fresh leaves SC-CO2 GC-FID 0.04–0.18 ppm (Yahya, 2011)
Fresh leaves SC-CO2 GC–MS 716.50 ng/g (Laohakunjit & Noomhorm, 2004)
Fresh leaves SC-CO2 RDA and HP TLC 7.163 ppm (Bhattacharjee et al., 2005)
Fresh leaves SC-CO2 GC–MS 0.04–0.18 ppm (Yahya, Lu, Santos, Fryer, & Bakalis, 2010)
Fresh leaves Organic SvE GC–MS 2771.10 ng/g (Laohakunjit & Noomhorm, 2004)
Fresh leaves SDE GC–MS 1.55 ng/g Laohakunjit and Noomhorm (2004)
Fresh leaves SDE RDA and HP TLC 0.965 ppm (Bhattacharjee et al., 2005)
Fresh leaves SDE GC–MS 10.26 ppm (Wongpornchai et al., 2003)
Fresh leaves SDE GC–MS 8.00 ppm (Thimmaraju et al., 2005)
Fresh leaves SDE GC–MS 3.10 ppm (Wakte, Nadaf, Krishnan, & Thengane, 2007)
Fresh leaves SlE GC–MS 0.21–0.52 ppm (Yahya, 2011)
Fresh leaves SlE GC–MS 0.06–0.45 ppm (Yahya et al., 2010)
Peanuts (Archis hypogaea) Processed seed oils HVDE HR GC-O and HR GC–MS – (Matsui et al., 1998)
Pearl millets (Pennisetum glaucum) Wetted ground SvE GC-FID – (Seitz, Wright, Waniska, & Rooney, 1993)
Popcorn Popped SlE HR GC–MS 24 µg/kg (Schieberle, 1991)
Potato (Solanum tuberosum) Extruded snacks HVDE using S-AFEvE GC–MS – (Majcher & Jelen, 2005)
Boiled SlED HR GC–MS – (Mutti & Grosch, 1999)
Pumpkin (Telfairia occidentalis) seeds Processed seed oils HVDE HR GC-O and HR GC–MS – (Matsui et al., 1998)
Roasted in-shell peanuts Fresh SvE using S-AFEvE GC–MS 1.92 mg/L (Kaneko, Sakai, Kumazawa, Usuki, &
Stored SvE using S-AFEvE GC–MS 0.462 mg/L Hishimura, 2013)
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Food Research International 130 (2020) 108924
Table 5 (continued)

Sources of 2-AP Sample Type Extraction Methods Quantification Methods Concentration Level References

Rye (Secale cereale) Breads crusts SvE HR GC-FID – (Schieberle & Grosch, 1985)
Breads crusts SDE SIDA 6.4 µg/kg
Sesame (Sesamum indicum) Roasted type SvED HR GC–MS 30 µg/kg Schieberle (1996)
Sorghum (Sorghum bicolor) Grains – Hs-GC with NPD 0.3019 ppm (Yundaeng, Somta, Tangphatsornruang,
Wongpornchai, & Srinives, 2013)
D.K. Verma and P.P. Srivastav

Soybean (Glycine max) Fresh seeds SvE GC–MS 0.2853 µg/g (Wu, Chou, Wu, Chen, & Huang, 2009)
Seeds – Hs-GC with NPD 579.5–1169.ppb (Arikit et al., 2011)
Calli in wild type – Hs-GC with NPD 325.3–457.3 ppb
Sweet corn (Zea mays convar. saccharata Cooked type High flow DHsS with TTP Capillary GLC-MS 4 µg/kg (Buttery, Stern, & Ling, 1994)
var. rugose)
Tobacco (Nicotiana tabacum) Cured leaves SDE GC–MS 0.02 µg/g (Peng, Sheng, Liu, Tong, & Liu, 2004)
Cured leaves SDSvE GC–MS 0.12 µg/g
Cured leaves HsCo-D GC–MS 0.11 µg/g
Wild mango (Irvingia gabonensis) Roasted seeds SvE and HVDE HR GC–MS – (Tairu, Hofmann, & Schieberle, 2000)
Winter melon (Benincasa hispida) Flesh SvE GC–MS 25.90 ppm Ruangnam et al. (2017)
Animals: Sources of 2-AP
Acha (Digitaria exilis Stapf) Cooked TTP GC–MS – (Lasekan, Feijao Teixeira, & Salva, 2001)
American lobster (Homarus americanus) Cooked tail meat DSvE and Vacuum SDE GC–MS Presented at below levels of (Lee, Suriyaphan, & Cadwallader, 2001)
detection limits.
Anchovy (Engraulis encrasicholus) Cooked ripened MDE GC–MS Trace amounts (Triqui & Reineccius, 1995)
Blue crab claw meat (Callinectes sapidus) Cooked type ASDE and Vacuum SDE GC–MS – (Chung & Cadwallader, 1994)
Boiled cod, salmon and trout Boiled SlE SIDA – (Milo & Grosch, 1996)
Carp fillet (Cyprinus carpio) Boiled carp extracts SlED HR GC-O 1.45–6.7 µg/kg (Schluter, Steinhart, Schwarz, & Kirchgessner,
1999)
Criollo cocoa beans Roasted type SvE GC–MS 4.2 µg/kg (Frauendorfer & Schieberle, 2008)
Egg yolk Heated type SDE GC–MS – (Cerny & Guntz, 2004)

14
Freshwater crayfish (Procambarus clarkii) Cooked tail meat Vacuum SDE GC–MS – (Cadwallader & Baek, 1998)
Hazelnuts (Corylus avellana) Roasted type Sensomics analysis Two-dimensional GC-TOF- 85 µg/kg (Kiefl, Pollner, & Schieberle, 2013)
MS with SIDA
Korean Mugwort (Artemisia princeps Leaves and stems SDE and HsSPME GC–MS and GC-O – (Choi, Cho, Kim, & Lee, 2014)
orientalis)
Licorice (Glycyrrhiza glabra) Peeled, dried, and chopped raw type SvE and HVDE using S-AFEvE HR GC-O and HR GC–MS 9.41 µg/kg (Wagber, Granvogl, & Schieberle, 2016)
Milk Fresh and Dried type L-LE using S-AFEvE GC–MS 0.0073 ng/g (Bendall, 2001)
Non-fat dry milk Heat-treated DSvE followed by HVDE GC–MS – (Karagul-Yuceer, Drake, & Cadwallader, 2001)
Parma ham Italian-type Dry-cured meat products HVDE using S-AFEvE GC–MS – (Blank et al., 2001)
Prawns Boiled SDE using modified LNEA GC–MS – (Morita, Kubota, & Aishima, 2001)
Rennet casein Commercial products of enzymatic DSvE followed by HVDE GC–MS – Karagul-Yuceer, Vlahovich, and Drake (2003)
precipitation of the casein from pasteurized
skim milk
Salami Italian-type Dry-cured meat products SlE GC–MS Unequivocally identified (Blank et al., 2001)
Sardines (Sardina spp.) Stored SvE and VDE GC-FID – (Triqui & Bouchriti, 2003)
Squid broth (Illex argentinus) Frozen HsSPE GC–MS 97.3 µg/kg (Carrascon, Escudero, Ferreira, & Lopez, 2014)
Sweet whey Fresh powder SvE and VDE using S-AFEvE GC–MS – (Mahajan, Goddik, & Qian, 2004)
Tempeh Fried fermented type SvE and VDE using S-AFEvE GC–MS 14–16 µg/kg (Jeleń, Majcher, Ginja, & Kuligowski, 2013)
Tuna Sauce Vacuum SDE GC–MS – (Cha & Cadwallader, 1998)
Microbes: Sources of 2-AP
Aspergillus awamori Liquid culture L-LE GC–MS 1.11 ppm Rungsardthong and Noomhoom (2005)
A. nigricans Liquid culture L-LE GC–MS 2.08 ppm
Bacillus cereus, Liquid culture SDE GC, GC–MS, GC-AED 0.030–0.087 ppm Romanczyk, McClelland, Post, and Aitken
(1995)
Liquid culture SDE GC–MS 0.0026–0.957 ppm (Adams & Kimpe, 2007)
Lactobacillus hilgardi Liquid culture L-LE GC–MS 0.025–0.320 ppm (Costello & Henschke, 2002)
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Food Research International 130 (2020) 108924
D.K. Verma and P.P. Srivastav Food Research International 130 (2020) 108924

chromatography; HsSPE: Headspace solid phase extraction; HsSPME: Headspace solid phase microextraction; HVDE: High vacuum distillation extraction; L-LE: Liquid-liquid extraction; LNEA: Likens–Nickerson extraction

extraction; SDE: Simultaneous/Steam distillation extraction; SDSvE: Simultaneous/Steam distillation and solvent extraction; SIDA: Stable isotope dilution assay; SlE: Soxhlet extraction; SlED: Soxhlet extraction with
chromatography-time-of-flight-mass spectrometry; GLC-MS: Gas-liquid chromatography-mass spectrometry; HP: High performance; HR: High resolution; HsCo-D: Headspace co-distillation; Hs-GC: Headspace-gas
Abbreviations: ASDE: Atmospheric SDE; DHsS: Dynamic headspace sampling; DSvE: Direct solvent extraction; GC: Gas Chromatography; GC-AED: Gas Chromatography with Atomic Emission Detection; GC-EOE: Gas
Chromatography-Effluent Odour Evaluations; GC-FID: Gas chromatography-flame ionization detector; GC–MS: Gas chromatography-mass spectrometry; GC-O: Gas chromatography–olfactometry; GC-TOF-MS: Gas

apparatus; MDE: Micro distillation extraction; NPD: Nitrogen-phosphorus detection; RDA: Rapid densitometric assay; S-AFEvE: Solvent-assisted flavour evaporation extraction; SC-CO2: Supercritical Carbon dioxide
plants (Gardner, 1988; Hatanaka, 1993). 2,4-decadienal is formed by β-
scission of 9-LOOH while the selective oxidation of 2,4-decadienal at
moderate temperatures produces the hexanal (Grosch, 1987). However,
(Munch, Hofmann, & Schieberle, 1997) report said that the similar aroma compounds are generated from oxi-
dation of linoleic acid and decomposition of 13-LOOH (Grosch, 1987).
(Grosshauser & Schieberle, 2013)

2-AP (i.e. popcorn aroma) have been found as the major aroma con-
tributor of raw rice (Champagne, 2008; Mahatheeranont et al., 2001;
Maraval et al., 2008; Tava & Bocchi, 1999; Zeng et al., 2008a, 2008b).
(Kim et al., 2000)

4.4. Rice cooked type


References

The stale flavor is detected in rice during cooking just after its
distillation; SvE: Solvent extraction; SvED: Solvent extraction with distillation; TLC: Thin layer chromatography; TTP: Tenax trap procedure; VDE: Vacuum distillation extraction.

storage at higher temperatures due to the free FAs synthesis and lipid
oxidation thereby forming the carbonyl compounds (Chikubu, 1970).
The VACs of cooked rice always differ from the VACs of uncooked rice
(Concepcion et al., 2018; Deng et al., 2013; Fukuda et al., 2014; Hinge
et al., 2016a, b; Park et al., 2010; Verma & Srivastav, 2016, 2018a; Xia,
Wang, Huang, & Li, 2016). There are some important factors which
Concentration Level

influence highly to the aroma of cooked rice. Among them, the im-
portant one is a genetic factor and second is conditions of pre- and post-
4.2–7.0 µg/kg

harvest which include drying, milling, and storage, etc. See, for in-
stance, VACs (especially 2-AP) affected by milling, resulted in higher
2.1 ppb

content is noticed in cooked rice compared to brown rice. However, this


compound is reported to decrease (extent up to 40–50%) during storage

while products of lipid oxidation are found increased (Champagne,


2008).
HR GC-O and HR GC–MS
Quantification Methods

The VACs of cooked rice have been studied by many researchers


with specific interest in the factors (Deng et al., 2013; Fukuda et al.,
2014; Lee et al., 2019; Liu, Zheng, Li, Zhao, & Xiong, 2007; Wu, Yang,
HR GC–MS

Chen, Jin, & Xu, 2011). The summary of some studies on VACs of dif-
ferent cooked rice samples is stated in Table 3. Therefore, several efforts
GC–MS

were taken to reduce or remove this particular off-flavor. For instance,


amino acids were added to boiling rice and Yamamoto and Kogure
(1969) found L-lysine hydrochloride effective in removing the stale
odor on account of the reaction of carbonyls with the amino group in
lysine which inactivates them. Furuhashi and Ayano (1971) conducted
Extraction Methods

SvE using S-AFEvE

a model system investigation and revealed the effectiveness of L-cy-


steine and L-histidine hydrochloride to regulate the rice odor during
Vacuum SDE

storage. The cooked fresh rice had 3–5 times higher volatiles compared
to stale cooked rice among which 80–90% volatiles had a lower boiling
SvE

point and this fraction is about 45% in stored rice (Aisaka, 1977). On
the other hand, the stored rice contained the C346 carbonyls which
accounted for 30% of total VACs − 10 times higher to fresh rice. In
previous reports, basic fractions representing the unique aroma of
Enzyme-hydrolyzed cooker effluent

cooked rice were shown by fractionation of the VACs of cooked rice into
acidic, neutral and basic fractions (Aisaka, 1977). A total of 40 com-
pounds were identified after varying degrees of milling in the cooked
Thermally treated extracts

rice aroma and reported a maximum volatile content in 92% of milled


rice, which decreased compared to increased milling (Tsugita, Kurata,
& Kato, 1980). This results in the conclusion that aroma of cooked rice
Pan-fried type

is caused due to the compounds from outer surface layers of rice. Pre-
Sample Type

vious reports showed 4.8 ppm of isolated volatile fraction in cooked


rice, of which 65% were in the acid fraction and 33% were in the
- Either in Trace amounts or Not Reported.

neutral fraction, while the basic fraction was below 1% (Yajima, Yanai,
Nakamura, Sakakibara, & Habu, 1978). In nutshell, out of total 100
identified compounds, over 90% of which were not identified in rice
White mushrooms (Agaricus bisporus)

previously.
The most common VACs of cooked rice are 2-AP, hexanal, octanal,
indole, (E)-2-nonenal, 4-vinyl-2-methoxyphenol and (E,E)-2,4-non-
adienal and out of which VACs, 2-AP is one of the more pronounced
Table 5 (continued)

odorants in cooked aromatic rice (Jezussek et al., 2002; Lee et al., 2019;
Liu et al., 2007; Mahattanatawee & Rouseff, 2008, 2014; Maraval et al.,
Sources of 2-AP

2008), non-aromatic rice (Jezussek et al., 2002; Lee et al., 2019;


Maraval et al., 2008; Park et al., 2010), black rice (2008b; Yang et al.,
Oyster

Yeast

2008a) and other cooked rice products viz. rice cake (Buttery et al.,
1999; Kurasawa et al., 1969). Interestingly, 2-AP was also reported in

15
D.K. Verma and P.P. Srivastav Food Research International 130 (2020) 108924

other plants, animals, and microbes during many studies. Studies on 2- et al., 2010); one was simultaneous/steam distillation and solvent ex-
AP in the case of the plant, animals, and microprobes are summarized traction (SDSvE), and another dynamic headspace sampling (DHsS).
in Table 5. The extracted VACs extracts were characterized by method ‘aroma ex-
Aseptic-packaging of cooked fragrant rice was used in an aroma tract dilution analysis (AEDA)’ and used GC-O for further evaluation. A
study conducted using by HS‐SPME/GC‐MS and the compound identi- total of 16 and 10 OACs with an average log3 of more than one flavor
fied as 2-AP was reported to be the most important contributor to the dilution (FD) were detected from the extracts of SDSvE and DHSS re-
overall aroma (Lee et al., 2019). While 2-acetyl-2-thiazoline (2-AT) spectively. In cooked non-aromatic rice of Korea, the record potent
reported as another compound using GC-PPFD, which was confirmed AACs were considered as 2-AP (popcorn-like aroma note) and 2-Methyl-
by the GC – MS TIC chromatographic standard retention value (Buttery 3-furanthiol (2-MF) (meaty like aroma note) exhibited higher log3 FD
et al., 1982; Mahattanatawee & Rouseff, 2008). The VAC, 2-AT was not by both SDSvE and DHSS extraction methods. Although, the thiol
observed in Jasmati or Basmati rice but it was detected in cooked compound, 2-MF was first identified which is one of the important
Jasmine rice as an additional impact aroma characteristics. A total of 30 aroma components of many food items which has already been proven
AACs were detected but only 27 VACs were identified. Five VACs were as a noteworthy odorant in the food (Hofmann & Schieberle, 1995).
detected as major AAC among 30 VACs, which were as follows: α-io- However, in the previous study, Park and co-workers used non-aro-
none, β-damascenone, β-damascone, geranyl acetate, and 3-methyl-2- matic Korean rice cultivar ‘Dongjin’ for studying sensory property of
butene-1-thiol. The VAC, 3-Methyl-2-butene-1-thiol was detected only cooked rice aroma and developed descriptive terminology. Boiled egg
in Jasmine rice responsible for the nutty and sulphury aroma. white flavor was reported by Park, Kim, and Kim (2001) as one of
(Semmelroch & Grosch, 1996). The aroma volatiles consists of alcohols, descriptive terminologies used to evaluate the aroma of cooked rice.
aldehydes, ester, heterocyclics, ketones, and sulfur compounds. Nu- Although, this descriptive terminology was also described by other re-
merically, the aldehydes comprised a major portion of all AACs in searchers but was as sulfury or sewer animal-like (Champagne et al.,
cooked rice followed by alcohols, esters, heterocyclics, ketones, and 1997; Meullenet, Marks, Griffin, & Daniels, 1999).
sulfur compounds. Other studies on VACs of cooked rice also stated that A group of researchers studied similarities and differences between
aldehydes were encompassed as the most observed group of VACs. the VACs of three different types of non-aromatic rice (viz. Shunyou,
(2008b; Yang et al., 2008a). There was no single VAC or set of VACs LGC-katsu, and LGC-soft) at four different times during cooking (Zeng
except for the concentration used to define a cultivar when comparing et al., 2008b). They identified a total of 77 VACs among which 13
VACs of cooked brown rice (three scented and one non-scented) compounds were not reported previously in rice. The main VACs were
(Jezussek et al., 2002). But, the compound 2-aminoacetophenone was 2-methoxy-4-vinylphenol, vanillin, indole, 2-pentylfuran, (E)-2-nonenal
considered to be an important odorant due to its highest dilution value and (E,E)-2,4-decadienal etc. These major VACs have already been
(DV). highlighted in previous reports as flavor molecular markers in rice.
A total of 35 VACs were identified in cooked black rice known as Time was the main factor found during observation which created the
aromatic specialty rice which has popularity among the Asian peoples major differences between the rice cultivars and VACs which had
due to its unique flavor (Yang et al., 2008a). The highest abundance emitted during cooking. Another group of researchers also compared 81
was 80.1% of the total relative proportion of aroma composition ex- volatiles aroma of different class viz. alcohols, aldehydes, fatty acids,
hibited by aldehydes and aromatics VACs. Higher concentration was fatty esters, heterocyclic, ketones, and phenolic, identified in the
seen in 2-AP which was exceeded only by hexanal, 2-pentylfuran, and cooked sample of three different types of rice associated with different
nonanal. The difference between the VACs of cooked white and black amylose content (Fukuda et al., 2014). The identified VACs of cooked
rice was strongly influenced by 2-AP, p-xylene, indole, and guaiacol. rice from aromatic (Aychade and Fidji) and non-aromatic (Ruille) cul-
The unique characteristics aroma of black rice was majorly contributed tivars also compared them with identified VACs of marketed Asian
by 2-AP (popcorn) and guaiacol (black rice-like, smoky) based on odor scented one (Thai) (Maraval et al., 2008). GC-O analyzed all four rice
thresholds, relative concentration levels, and olfactometry among the extracts resulted in the perception of 40 OACs. 2-AP and oct-1-en-3-one
identified 25 OACs. In another study, cooked non-aromatic rice of were two VACs which almost always perceived. While GC–MS identi-
Korea (‘Jeongilpum’) analyzed using GC-O to evaluate OACs. A 25 fied and quantified 60 compounds in which some of them were a few
odorants out of 36 were an intermediate or of greater odor intensity new OACs.
(≥3) from six manifestly different rice flavor types viz. basmati, jas- Cooked Japonica rice (Wuchang) and Jasmine rice (Complete
mine, two Korean japonica cultivars, black rice, and a non-scented rice Wheel) for volatile profile were investigated and reported a total of 77
(Yang et al., 2008b). The odorants deemed as major OACs were only 13 compounds of different class viz. aldehydes (20), alcohols (16), ketones
as follow: (E)-2-nonenal (beany, cucumber), (E)-2-octenal (nutty, (14), arenes (9), esters (7), alkanes (5), olefins (3) and hetero-cycle (3)
cooked flour), (E,E)-2,4-decadienal (fatty), (E,E)-2,4-nonadienal (nutty, (Deng et al., 2013). Among all identified VACs, major were 1-hexanol,
fatty), 1-octen-3-ol (mushroom), 2-AP (popcorn), 2-heptanone (fruity, 1,10-biphenyl,2,20,5,50-tetrameth1-heptanol, 1,3-hexadiene, 1-non-
sweet), decanal (citrus), guaiacol (black rice-like, smoke), heptanal anol, 1-octen-3-ol, 1-octanol, 2,4-decadienal, 2-AP, 2-heptanone, 2-
(floral), hexanal (green tomato, green), nonanal (citrus, fatty), and heptenal, 2-methyl-2-ethyl-3-hydroxyhexyl, 2-methyl-2-nonen-1-ol, 2-
octanal (citrus). These 13 odorants among the six distinctly flavor types nonanone, 2-octenal, 3-(3-methyl-1-butenyl)-(E), 3,4-diethox-
were the primary VACs thought to describe the differences in the ybenzaldehyde, 3-ethyl-2-methyl, 3-nonen-2-one, 3-nonen-5-yne, 3-
aroma. Yang et al. (2008b) similarly suggested as many of the re- octen-2-one, 4-ethyl, 6,10-dimethy-5, 6,7-dodecanedione, 7-methoxy-
searchers pointed out that 2-AP was not a single compound to explain 2,2,4,8-tetramethyltricyclo, 9-undecadien-2-one, cyclohexene, di(iso-
cooked rice aroma, although overall aroma composition was delineated butyl), glutaric acid, hexanal, isobutyl 3-methylbu, nonanal, pentade-
by the result of combine mixture of many VACs. In the study of Yang cane, phthalic acid, propanoic acid, and tetradecane. In the recent study
et al. (2008b), 1-octen-3-ol had highest odor intensity (2.7 ng/L) fol- of Xia et al. (2016), the germinated brown rice (GBR) of two varieties
lowed by order guaiacol (1.5 ng/L) and 11 aldehydes (0.09–3.1 ng/L) (viz. JZDG and CMSG) was used due to the impressive health-promoting
while 2-AP exhibited lowest odor intensity (0.02 ng/L). The values of effects. GBR has increased the popularity as functional food among the
odor intensity for (E)-2-nonenal, 2-AP, heptanal, hexanal, nonanal, and peoples (Heiniö et al., 2016). From cooked GBR, total detected VACs
octanal were comprised of more than 97% of relative odor intensity were 35, which belong to aldehydes and alkanes as a major class of
concentration from each flavor rice, even though the relative con- identified VACs. Among the identified VACs, most were detected in
centration varied among samples. JZDG, follow as (E,E)-2,4-decadienal, 2-carene, 2-methyl-1-penten-3-
One other study on the aroma of cooked non-aromatic rice of Korea, one, 2-n-heptylfuran, 3,3,5-trimethyl-cyclohexene, 4-decanone, 4-me-
two extraction methods were considered to study potent AACs (Park thyl-1,5-heptadiene, 6-methyl-5-hepten-2-one and cyclotetradecane,

16
D.K. Verma and P.P. Srivastav Food Research International 130 (2020) 108924

while some of them as 2-methoxy-4-vinylphenol, 4-methyl-(Z)-2-pen- rice including California Brown Pearl rice, black and red Japanese rice
tene, and 2,6,10-trimethyl-dodecane presented in CMSG. Identified hydrodistillate bran extracts and Basmati, Jasmine, Australian fragrant,
VACs viz. 2-pentyl-furan, hexanal, and pentanal exhibited relatively and non-fragrant rices extracts contained almost all these terpenoids
higher concentration (Xia et al., 2016). (Sukhonthara, Theerakulkait, & Miyazawa, 2009; Tsugita et al., 1978;
Widjaja et al., 1996a). The KDML 105 white rice bran contained a
5. Aroma in different products of rice major amount of α-neo-carvene - caraway odorant whereas the lack of
non-glutinous rice bran of cultivars: BT No.3 and Hom Nin possessed
5.1. Rice bran the essential oils of marjoram containing Sabinene (Reverchon, 1992).
All rice bran samples except BGMSN contained β-cymene, found max-
Rice bran is the low-cost by-product of rice consisting of 5–8% of imum in Samoeng black rice bran (Sukhonthara et al., 2009). Terpe-
total rice grain weight. It is industrially employed to extract the oil, as noids are made up of isoprene units which are generated from dehy-
animal feed and an organic fertilizer (Silva, Sanches, & Amante, 2006); drogenation of α-terpinene represent the volatile compounds found in
however, its consumption is very less due to distinct odor (Fujimaki nature. 1,8-cineol – found only in Hom Nin and BT No.3 black non-
et al., 1977) and several studies were undertaken to explore the con- glutinous rice bran possesses a fresh, spicy and camphor-like aroma
stituents of rice bran VACs. Nine common alcohol and eight carbonyls while the BGMSN contained the metabolic product of limonene - Car-
were found in rice bran after flushing with N2 gas for 4 h but none of veol (Degenhardt, Köllner, & Gershenzon, 2009). Likewise, Hom Nin
them was directly associated with the aroma of rice bran (Mitsuda, black non-glutinous rice bran contains α-pinene and β-form of pinene
Yasumoto, & Iwami, 1968). 4-vinylguaiacol and 4-vinylphenol were the were found in Jasmine KDML 105 white non-glutinous rice bran. Thus,
main identified VACs offering a distinctly unpleasant odor among 170 these two monoterpenes were identified in the cultivar BT No.3-hybrid
identified compounds out of more than 270 detected compounds between Hom Nin and Jasmine KDML 105 like camphor (having a
(Fujimaki et al., 1977; Tsugita et al., 1978). Further, rice bran like pungent odor) and camphene, the Hom Nin contains fenchyl acetate.
volatiles was also possessed by neutral fraction, totally identical to All these monoterpenoids are generated from precursor α-terpinyl ca-
whole volatile concentrate and two phenols discussed above were the tion which was present in black non-glutinous Hom Nin rice bran
major volatiles identified which provides aroma to cooked rice as well (Degenhardt et al., 2009). Further, all rice bran contained a phenolic
as steam-distilled rice bran (Fujimaki et al., 1977). Interestingly, the aldehyde - vanillin whose maximum amount was found in Jasmine
researchers found that thermal decarboxylation of ferulic and p-cou- KDML 105 rice bran. Studies have also revealed the presence of palmitic
maric acids may result in the formation of 4-vinylphenol and 4-vi- acid, hexahydrofarnesyl acetone, and phytol as the major VACs in the
nylguaiacol which were present in free-form in rice (Fiddler, Parker, straw of rice (Miyazawa, Nagai, & Oshima, 2008).
Wasserman, & Doerr, 1967; Houston, Hill, Garret, & Kester, 1963). The The black and red rice bran showed the presence of 129 VACs (red
thermal decomposition of lipids may generate lactones while the rice bran-95.01% and black rice bran-94.79%) acids followed by alde-
thermal dehydration of thiamin or heat-based interaction between hydes in volatile oil (Sukhonthara et al., 2009). Red rice bran had more
carbonyl compounds and sulfur-containing amino acids formed the hexanal than black rice bran. Red rice bran contained the higher
thiazoles, especially 2-acetylthiazole which are responsible for the amount of (2E)-decenal, (2E)-nonenal, (2E)-octenal, (2E,4Z)-dec-
aroma of rice bran (Maga & Katz, 1975, 1976; Maga, 1978; Tsugita adienal, 1-octen-3-ol, 2-heptanone, 2-methylnaphtalene, benzaldehyde,
et al., 1978). Another objectionable VAC linked with rice bran is di- naphthalene, nonanal, and octanal; however black rice bran was rich in
methyl sulphide, produced from S-methylmethionine sulfonium n-pentanol, isovaleric acid, valeric acid, enantic acid, guaiaol, caproic
chloride (Namba, Ohba, Kitamoto, Hirasawa, & Karahashi, 1982). acid, myristic acid, and pelargonic acid. The major odorant found in
Rice bran contains limonene – monoterpene, the dominating black rice bran was guaicol (0.81 mg/100 g) which produces a smoky
odorant possessing the citrus-like odor which was detected in head- aroma in cooked black rice (2008b; Yang et al., 2008a).
space extracts of two aromatic rice cultivars of South China, cooked
black rice and steam distilled cooked white rice extract (Goufo, Duan, 5.2. Rice cake
Wongpornchai, & Tang, 2010; Yajima et al., 1978, 1979; Yang et al.,
2008a). However, the bran of white Jasmine rice KDML 105 rice con- Rice cake is an important bakery product, developed from rice flour
tained the maximum amount of β-cymene, and trans-β-ocimene which derived from long- and medium-grained type brown rice. The quality
were otherwise found in all studied samples of rice bran whereas the attributes of rice cakes are influenced by different factors like heating
black rice bran samples possessed the myrcene – a significant inter- temperature, heating time and tempering moisture (Kim, Lee, Hsieh, &
mediate compound important for the synthesis of several volatiles. The Eun, 2001). Very few studies on VACs of rice cake are available in the
myrcene is therefore found as an essential aroma compound that pro- literature and presented in Table 3. The VACs obtained from extraction
vides an herbaceous odor to black rice. The major oxygenated mono- of rice cake using hot water include the 2-methylpropanal, 3-methyl-
terpenes detected included the linalool and cis- and trans-linalool oxide butanal, ammonia, ethanal, hexanal, hydrogen sulfide, and propanal
among the oxygenated monoterpenoids group. These oxygenated (Kurasawa et al., 1969). The authors confirmed the presence of original
monoterpenoids were found in brans of rice: black non-glutinous Hom rice cake identical aroma from synthetic mixture which contained the
Nin, BD and 16,083 as well as KDML 105 rice. These cultivars contain aldehydes in same amount present in the product together with hy-
nearly 10 times higher concentration of limonene and cis-linalool oxide drogen sulfide and ammonia. The characteristic odor of 2-propionyl-1-
compared to other cultivars. These monoterpenoids offer a floral sweet pyrroline was detected by GC–MS. 2-AP had been first found as an
and fruity aroma thus improving the rice aroma quality. Further, rice important VAC of aromatic rices (Buttery et al., 1988), and its occur-
bran also contains trans-caryophyllene – a sesquiterpene, usually found rence in rice cakes was expected. However, the mechanism of its for-
in spicy and dry odorant of clove oil, however, its concentration was mation at the high-temperature conditions used while preparing rice
very less compared to 7-epi-α-selinene and α-neo-carvene normally cakes may be different from that involved in boiled rice. Alkyl pyrazines
found in KDML 105 bran (Ghelardini, Galeotti, Di Cesare Mannelli, are common in most food products cooked at temperatures well above
Mazzanti, & Bartolini, 2001). Some rice cultivars contain the maximum 100 °C and are also present in rice cakes. These were similar to those
of minor terpenoids such as α-elemene, α-gurjunene, and terpinen-4-ol found in popcorn qualitatively but different quantitatively. The most
were present in black glutinous rice bran only which may contain other important VACs were 2-ethyl-3,6-dimethylpyrazine and 2-ethyl-3,5-di-
terpenoids also. like β-bisabolene, camphor, camphene, 1,8-cineol, α- methylpyrazine, Further, the moderate concentrations of Strecker de-
copaene, estrageol, fenchyl acetate, menthol, α-pinene, sabinene, α- gradation products 2- and 3-methylbutanal and phenylacetaldehyde are
ylangene, and trans-cadina-1(6),4-diene. Several natural and processed found in the rice cakes. The lipid autoxidation synthesizes the hexanal

17
D.K. Verma and P.P. Srivastav Food Research International 130 (2020) 108924

at a moderately high concentration in rice cakes (Buttery et al., 1999). its aroma like togwa - fermented maize-sorghum gruel from Tanzania
Aliphatic acids were also identified in the volatiles of brown rice which (Hansen & Schieberle, 2005; Mugula, Narvhus, & Sorhaug, 2003). The
is used to prepare the rice cakes. They had been also found in popcorn major compound responsible for the khanom jeen aroma is diacetyl in
but they are relatively weak odorants in other products (Buttery, Stern, terms of OAV in addition to low concentration of 3-methylbutanal and
& Ling, 1997). These are present below their water threshold con- benzaldehyde - straight-chain aldehydes, generated by fermentation.
centration level in rice cakes. Among aldehydes, the 3-methylbutanal exhibited the highest OAV and
this malty compound was reported in several fermented cereal products
5.3. Soong-neung previously (Czerny & Schieberle, 2002; Mugula et al., 2003).

A rice-based beverage - Soong-neung is a traditional drink from 5.5. Rice wine


Korea and prepared from roasted and cooked rice which is consumed
after meals. Roasting performed at 125–155 °C produces the volatiles - Rice wine is a traditional alcoholic drink that is very popular in
carbonyls and pyrazines associated with this product (Cheigh, Nam, China possessing higher nutritional value and distinct aroma (Chen &
Kim, & Kwon, 1975; Nam, Cheigh, & Kwon, 1973). A few compounds Xu, 2010; Jung, Lee, Lim, Kim, & Park, 2014). It contains 15 VACs
were characterized and identified by GC–MS out of them, a total of only including 10 esters and 5 higher alcohols similar to rice. The wine has
five compounds from pyrazine fraction as follows; 2-ethyl-5-methyl- fruity and floral aroma due to the presence of esters whereas the al-
pyrazine, 2-ethyl-3-methylpyrazine, 2,3-dimethylpyrazine, 2,5-di- cohols contribute to the aroma of freshly brewed rice wine (Erten,
methylpyrazine, and 2-methylpyrazine were identified positively. The Tanguler, & Cakiroz, 2007). Among alcohols, ethanol is the dominating
compounds of pyrazines class were perhaps formed during the roasting along with other higher alcohols in rice wine and fermented or stored
process. The compounds, 2,3-dimethylpyrazine and 2,5-dimethylpyr- wine contained the following alcohols: 1-propanol, butanediol isoamyl
azine of pyrazine fraction was one of the impact aromas of Soong-neung alcohol, isobutanol, and phenethyl alcohol (Luo, Fan, & Xu, 2008). On
which is associated with the nut-like or roasted cereal-like aroma of the other side, the isobutanol carries the faint smell of allyl alcohol with
food. Whereas from carbonyls fraction, compounds viz. acetaldehyde, slight bitterness whereas the isoamyl alcohol possesses a banana flavor
iso-butyraldehyde, iso-valeraldehyde, and propionaldehyde were which decreases the leucine – a bitter amino acid for improving the
identified positively (Cheigh et al., 1975; Nam et al., 1973). wine taste. Similarly, phenyl ethanol is present in a significant amount
in Chinese rice wine which contributes to the rosy and honey aromas
5.4. Khanom jeen (Chen & Xu, 2010).
Makgeolli is a traditional Korean rice wine that has been consumed
Among the people in Southeast Asia, there are many types of rice by Koreans for many centuries. The associated predominant VACs are
products are consumed in which rice noodles are well known as follow as 2-methoxy-4-vinylphenol, 2-phenethyl acetate, 3-methyl-1-
common products of rice (Cham & Suwannaporn, 2010). Khanom jeen butanol, diethyl succinate, ethanol, ethyl 9,12-octadecadienoate, ethyl
is one kind of traditional noodle prepared from slight fermentation of acetate, ethyl decanoate, ethyl dodecanoate, ethyl hexadecanoate, ethyl
rice (Keatkrai & Jirapakkul, 2010; Pisitkul & Rengpipat, 2014). The octanoate, ethyl tetradecanoate, and ethyl(Z)-octadec-9-enoate (Jung
qualities of rice are very important in making much better noodles et al., 2014). The VACs viz. 2-methyl-1-propanol, 2-methylbutan-1-ol,
preparation which plays an essential role in noodle quality. Generally, 2-phenethyl acetate, 2-phenylethanol, 3-methylbut-1-ylethanoate,
rice varieties with high amylose have more useful compare to rice ethanol, ethyl acetate, ethyl butanoate, ethyl hexanoate, ethyl oc-
varieties of low amylose content because such rice varieties have played tanoate, isobutyl acetate, and propan-1-ol have also been identified in
a well role in noodle preparation (Cham & Suwannaporn, 2010; sake, a Japanese rice wine (Kiyoshi, 1999). Thirty-three esters con-
Jobling, 2004). There are two types of Kanom-jeen commercially stituted the largest group among the 45 detected VACs. Among them,
available in the markets throughout Thailand; they are as follows (1) 10 esters (2-phenethyl acetate, 3-methylbut-1-ylethanoate, ethyl (Z)-
fermented, and (2) non-fermented. Consumer’s choice on fermented octadec-9-enoate, ethyl 9,12-octadecadienoate, ethyl acetate, ethyl
Kanom-jeen because of this food exhibits characteristic fermented decanoate, ethyl dodecanoate, ethyl hexadecanoate, ethyl octanoate,
flavor and unique textural properties resulting in wide consumption by and ethyl tetradecanoate) were predominant VACs (Jung et al., 2014).
choice of Thai peoples in the country as well as outside of the country Among the 7 alcohols, ethanol, 2-phenylethanol, and 3-methyl-1-bu-
(Keatkrai & Jirapakkul, 2010; Pisitkul & Rengpipat, 2014; tanol were the dominant compounds. These alcohols have been con-
Rojanaphaiboon, 1987). sistently detected as major VACs of Korean rice wines by different ex-
Khanom jeen exhibited 43 compounds in VACs of samples using traction and analysis methods (Kim et al., 2008a, 2010).
GC–MS where the alcohols were dominating contributing to 73% of
total volatiles followed by acids (18%) and ketones (7%) (Keatkrai & 6. Extraction, identification and quantification methods
Jirapakkul, 2010). 1-propanol was the most prevalent alcoholic com-
pound found in the headspace of khanom jeen sample volatiles in ad- The extraction process is generally the step at which most analyte
dition to 2-butanol, ethanol, and 3-methyl-1-butanol. However, these loss occurs; therefore, efficient methods of extraction are continually
aroma compounds contributed very less to the overall aroma due to being sought (Choi et al., 2019; Verma & Srivastav, 2016; Verma,
their higher odor threshold level but are significant because of inter- Mahato, & Srivastav, 2018d; Xia et al., 2016). It is important to assess
action among odors in the mixture (Grosch, 2001). The short-chain the VACs for the extraction, identification, and quantification of VACs
aliphatic acids except for 2-methylpropanoic acid and 3-methylbuta- from rice by different methods viz. extraction, identification, and
noic acid caused due to lipid oxidation and thermal decomposition were quantification. There is no single method that will prove optimal for
reported in aroma of rice (Zeng, Zhang, Chen, Zhang, & Matsunaga, aroma extraction, identification, and quantification of rice. In this
2007). The aroma of compounds: 2-methylpropanoic acid and 3-me- order, several traditional and modern methods are available for ex-
thylbutanoic acid contributes to ‘cheesy’ and ‘sweaty’ aroma, which traction and isolation of rice aroma chemicals which are coupled with
were also reported in sourdough bread and other cheeses (Curioni & analytical methods (Table 6). These analytical methods were studied
Bosset, 2002; Czerny & Schieberle, 2002; Kirchhoff & Schieberle, 2002). and have been used for identification, characterization, and quantifi-
In addition to these, many carbonyl compounds were identified and cation of rice VACs at different levels of concentration ranges from 1 to
samples of Khanom jeen rice contained the 2-butanone, diacetyl, and 10 ppb level to 3 ppm from different sample matrix of rice and its
acetoin among which the latter two ketones possess buttery aroma. The products (Bergman et al., 2000; Bryant et al., 2011; Buttery et al., 1988;
fermentation-derived, sourdough bread usually carries these ketones in Buttery, Ling, & Mon, 1986; Grimm et al., 2011; Grimm et al., 2001;

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D.K. Verma and P.P. Srivastav Food Research International 130 (2020) 108924

Table 6
Methods for extraction, identification, and quantification of rice VACs.
(A) Traditional and Modern Methods for Isolation and Extraction

(1) Traditional Methods


Purge and trap
Simultaneous steam distillation
Micro steam distillation
Direct solvent extraction
(2) Modern Methods
Solid-phase microextraction
Supercritical fluid extraction with CO2
(B) Analytical Methods for Identification and Quantification
Gas chromatography-mass spectrometry (GC–MS)
Gas chromatography-mass spectrometry with flame ionization detection (GC–MS-
FID)
Gas chromatography-mass spectrometry with alkali flame ionization detection
(GC–MS-AFID)
Gas chromatography-mass spectrometry with flame thermionic detection (GC–MS-
FTD)
Gas chromatography-mass spectrometry with selected ion monitoring (GC–MS-SIM)
Capillary gas chromatography-mass spectrometry (Capillary GC–MS)
Gas chromatography–olfactometry (GC-O)
Gas chromatography-flame ionization detection (GC-FID)
Gas chromatography-pulsed flame photometric detection (GC-PFPD)
Gas chromatography-time-of-flight- mass spectrometry (GC–TOF–MS)
Gas-liquid chromatography (GLC)
Gas-liquid chromatography with capillary or packed column (GLC-Capillary or GLC-
Packed column)

Hinge et al., 2016a, b; Khorheh et al., 2011; Peddamma et al., 2018;


Sriseadka, Wongpornchai, & Kitsawatpaiboon, 2006; Wongpornchai
et al., 2004; Yoshihashi, 2002).

6.1. Isolation and extraction methods

For extraction of VACs from sample matrix of various rice and rice’s
products have been studied by using different isolation methods and
arises from a cocktail of over 500 compounds of different chemical class
Fig. 1. Likens Nickerson simultaneous distillation extraction apparatus
viz. alcohols, aldehydes (aliphatic and aromatic), hydrocarbons (al-
(Sunthonvit et al., 2005).
kanes, alkenes, aromatic), carboxylic acids, esters, furans, ketones, N2-
containing, phenols, sulfur-containing, and terpenes have been identi-
fied. A particular molecule of note is 2-AP which has been shown to be microextraction (SFME) and supercritical fluid extraction (SFE) are the
the predominant OAC in sample matrix of various rice and rice’s pro- most important and common procedures (Table 3) coupled with GC–MS
ducts at concentrations of several hundred parts per billion (ppb) that reported in the literature on VACs. The impact of chemical character in
emitting a popcorn-like aroma, found in all rice plant parts except roots rice is to be identified by the classical methods of the 21st century. The
(Yoshihashi, 2002), is also present in non-aromatic rice (Bryant & work details of each method used as extraction methods by many re-
McClung, 2011; Hinge et al., 2016a, b; Mathure et al., 2014; Park et al., searchers are presented in the following sections, as they are:
2010; Setyaningsih, Majchrzak, Dymerski, Namieśnik, & Palma, 2019).
Zhou, Robards, Glennie-Holmes, and Helliwell (1999) reviewed the 6.1.1. Simultaneous distillation extraction
methods viz. direct extraction, distillation, and headspace for VACs Simultaneous distillation extraction (SDE) is an important extrac-
analysis and their contribution to flavor in cereals in which headspace tion method (Fig. 1) for VACs, merges vapor distillation and solvent
complemented by solid-phase microextraction (SPME) and it has be- extraction so as to simplify experimental procedures (Chaintreau,
come one of the best isolation and extraction methods. The typical 2001). In these methods, the final product is a solvent extract. SDE is
concentration levels (in ppb) of different VACs from rice were: alcohols also known as the Likens–Nickerson steam distillation, more popular
1869, aldehydes 5952, disulfides 79, heterocyclic compounds 1220, among the all known methods for rice aroma chemical analysis. This
hydrocarbons 548, ketones 234, phenols 534 and terpenes 257. The method was first reported by Likens and Nickerson (1964) and then
discussed methods have been employed for the extraction of aroma modified by Sunthonvit, Srzednicki, and Craske (2005) for studying
volatiles that affects considerably on the quality and quantity of rice VACs of rice. SDE has been one of the most often cited methods for the
(Sriseadka et al., 2006). Weber et al. (2000) reported that one of the isolation of volatiles since its first report in 1964 (Chaintreau, 2001). In
major limitations is the lack of a quantitative assay in improvement of previous many studies, SDE widely used to analyze VACs from a dif-
scented rice for aroma through breeding because; there is no method to ferent type of rice viz. aromatic and non-aromatic by many researchers
quantify relative proportion of the concentrations of different VACs or (Table 3).
activity of some critical enzyme. Many researchers worked on best Buttery, Ling, Juliano, and Turnbagh (1983b) determined the con-
analytical methods for extraction and isolation of rice VACs. In order to centration of 2-AP in the steam volatile oils of 10 different varieties of
get higher extraction yield (referred as high efficiency) and potency of rice varied from less than 0.006 to 0.09 ppm for Calrose and Malagkit
the extract (referred as efficacy), researchers have made considerable Sungsong rice varieties respectively which was based on the dry weight
effort to find efficient methods for extraction of VACs for rice aroma. of the rice. Later, Buttery et al. (1986) used SDE to extract VACs from
Currently, simultaneous distillation extraction (SDE), solid-phase 200 g of rice for quantification of 2-AP in rice samples and showed that

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D.K. Verma and P.P. Srivastav Food Research International 130 (2020) 108924

Fig. 2. Process flow chart and block diagram of SPME set-up coupled with GC–MS for extraction of rice aroma volatile compounds (Grimm et al., 2001; Pawliszyn, 2001).

method was sufficiently accurate for quantitative analysis of 2-AP in Buttery et al. (1986) was to establish a practical, simple method for
rice. extracting and isolating rice VACs. The results showed that rice sample
A comparative study was made by Widjaja et al. (1996a) by using possessed a well-known 2-AP concentration level with this established
the SDE method to conduct a comparative study on the VACs of fragrant method and found a method best suited for quantitative analysis of 2-
and non-fragrant rice. In the same year again used the SDE method by AP from rice sample. While, Widjaja et al. (1996b) used the SDE
Widjaja et al. (1996b) to conduct another study. This study was in method for explaining variations of VACs in rice samples during storage
storage condition to know the changes in VACs of paddy, brown and condition. After a critical discussion of these key findings and other
white fragrant rice and observed the level of total VACs in all three researchers' reports on the benefits and important features of the SDE
forms of rice was increased. Another comparative study was made by method, it can be concluded that (1) the variations between volatile
Laksanalamai and Ilangantileke (1993) by using SDE method to identify compounds and non-volatile compounds found in the rice sample may
the 2-AP, an impact VAC in fresh and aged (shelf-stored) Khao Dawk be exploited. The SDE technique was selected to enhance the extraction
Mali (KDML) 105 (a well-accepted scented Jasmine type indica rice of rice volatile aroma compounds, as well as to restrict or exclude non-
variety Thailand), in non-scented rice, and in leaves of pandan (Pan- volatile components which do not have any significance and only cause
danus amaryllifolius). obstruction during study. (2) The extraction period is a good analytical
A total of 100 VACs were isolated by Petrov et al. (1996) from factor. Rice processing usually takes 1–4 h. The extraction efficiency is
scented rice and non-scented rice in cooking water using the SDE always highest in the SDE technique due to the solvent nature and the
method. Identification and quantification of volatile compounds from extraction period. This is the main reason why scientists are trying to
commercial basmati and Italian rice samples were performed by Tava find the best experimental conditions for the recovery of the selected
and Bocchi (1999) by using the SDE method. volatile rice aroma components. Therefore, in further study and ana-
A study by Bhattacharjee et al. (2003) on the extraction of VACs lysis of rice aroma, the SDE method can be applied which gives a dif-
from a popular commercial brand of Basmati rice was evaluated by ferent perspective.
using Likens–Nickerson extraction and supercritical fluid extraction
(SFE) with carbon dioxide (CO2). The study reported the advantages of 6.1.2. Solid-phase microextraction
smaller sample size, shorter time of extraction and the negligible pos- Solid-phase microextraction (SPME) is a relatively and rapidly
sibility of artifacts with the SFE method merit, its use for recovery of emerging as a new robust solvent-free, simple, rapid sampling method
aroma volatiles from Basmati rice. A modified Likens and Nickerson to implement, low cost, ease of operation, sensitive and reliable method
apparatus by Sunthonvit et al. (2005) for the extraction of volatiles for among the all methods (Djozan & Ebrahimi, 2008; Kaseleht, Leitner,
from Thai fragrant rice varieties in which SDE was combined with a & Paalme, 2011; Verma, Mahato, Billoria, & Srivastav, 2018a; Zhou
distillation-extraction unit (Fig. 1). Park et al. (2010) used SDE method et al., 1999) that can overcome the difficulties and can be applied to the
to detect VACs from cooked Korean non-aromatic rice. detection of flavour volatiles (Zhang, Yang, & Pawliszyn, 1994) from a
However, the perspectives of researchers were quite different be- variety of matrices by partitioning them from a liquid or gaseous
hind the use of the SDE method. For instances, the aim of the study of sample matrix into a polymeric liquid coating i.e. an immobilized

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D.K. Verma and P.P. Srivastav Food Research International 130 (2020) 108924

stationary phase (Steffen & Pawliszyn, 1996). SPME uses a very simple
setup and requires no additional instrumentation other than a con-
ventional GC with the traditional injection port (Djozan & Ebrahimi,
2008; Steffen & Pawliszyn, 1996) shown in Fig. 2. The device consists of
two separate steps, step first: deals with partitioning the target analytes
between the sample matrix and the fiber surface, whereas the second
deals with the direct desorption of absorbed analytes into injection port
by means of GC (Djozan & Ebrahimi, 2008). In the SPME method to
collect the volatiles from the sample, it involves the use of fused silica
fiber (1 or 2 cm in length), which is very well defined in cylindrical
surface geometry. This configuration allows easy assessment of analyte
to and from the surface. This fiber is coated with a thin polymeric film
which is known as an extracting phase. Such a phase may be a solid or a
liquid comprised of a variety of conventional stationary phases. The
chemistry of VACs may decide their behaviors of adsorption and des-
orption on a particular type of fiber. Analytes varied in polarities may
require different fiber chemistries. In the market, there are a range of
fibers viz. polar, non-polar and mixed are available and have been
considered previously (such as polyacrylate (PA), carboxen, poly- Fig. 3. Application of solid-phase microextraction (SPME) in various fields viz.
dimethylsiloxane (PDMS) and divinylbenzene (DVB) as the commonly forensic perspective, environmental, biological, pharmaceutical, field analyses,
used types) in SPME methods to maximize its potential applications. and fragrance & aroma study.
Generally, the types of fiber to be considered depending on the com-
pounds that desired to be extracted from a sample (Arthur & Pawliszyn, solvent-free and no solvent contaminants in the Japanese rice cultivar
1990; Pawliszyn, 1997). The volatiles analytes can be extracted from Akitakomachi. A modified HsSPME/GC–MS was employed to analyze
different kinds of media in either the liquid or gas phase. SPME elim- the volatile profile of following rice cultivars from Japan: Nihonbare,
inates pre-concentration steps by directly extracting the analytes into a Koshihikari, & Akitakomachi during cooking and other rice cultivars
poly (dimethylsiloxane)-coated fiber with liquid polymer or solid sor- having lower amount of digestible protein during cooking (Zeng et al.,
bent during extraction followed by desorption into the chromato- 2008a, 2008b). A single HsSPME/GC–MS was used by Zeng et al.
graphic mobile phase for analysis (Arthur & Pawliszyn, 1990; (2009) to study the glutinous rice during cooking for the identification
Pawliszyn, 1997; Steffen & Pawliszyn, 1996). of VACs.
SPME was introduced in the 1990s (Yang & Peppard, 1994) and In 2010, Lin, Fan, Gao, Wu, and Wang (2010) presented a paper to
developed by Arthur and Pawliszyn; and Pawliszyn (1997; Arthur & demonstrate the efficiency of HS-SPME together with GCMS on VACs
Pawliszyn, 1990; Pawliszyn, 1995) in the early 1990s which can be study in 10th International Working Conference on Stored Product
used in both in the laboratory and on-site. Since, its introduction has Protection. Until that time, SPME was used solely for the study of rice
been used to analyze volatiles due to some advantages, such as simple, aroma and their efficacy, but later a new revolution began to be used
rapid, solvent-free, inexpensive, and less time for extraction when for a specific purpose in the rice aroma study; here are some examples
compared with other methods like SDE (Djozan & Ebrahimi, 2008; of such studies. Tananuwong and Lertsiri (2010) used SPME/GC–MS to
Zhang et al., 1994), has been considered as one of the most brilliant monitor the changes in key VACs of organic red fragrant rice cv. Hom
inventions as a simple, efficient and environment friendly method by Daeng during storage under different conditions. While, Goufo et al.
many researchers in the field of sample preparation in recent years. (2010) used HsSPME and static headspace in conjunction with GC–MS
Several studies have been published on the analysis of rice VACs using to investigate two fragrant rice (O sativa L.) cultivars viz. Guixiangzhan
SPME and many VACs have been identified (Table 3), and also have and Peizaruanxiang, grown in South China. The findings indicated that
gained popularity among scientists and researchers with the presence of manipulating pre- and post-harvest treatments can greatly improve the
advantages in its application in various fields (Fig. 3). specific attributes of the domestically produced cultivars and reported
In a study, 2-AP screened in the headspace of carboxen/DVB/PDMS China could effectively increase its share of the domestic market of
fiber using SPME on on twenty-one experimental rice varieties (Grimm fragrant rice and even tap into the international market (Goufo et al.,
et al., 2001). Another study by Monsoor and Proctor (2004) reported 2010). In another example, a combined GC–MS with the HsSPME
that SPME was employed to analyze the VACs of commercial samples of method used by Khorheh et al. (2011) for assessment of flavor volatiles
milled heads and broken rice. Bryant et al. (2006) conducted experi- of Iranian rice cultivars including two modified Iranian rice cultivars
ments for texture profile and VAC analyses of ‘koshihikari’ and ‘bas- and Hashemi rice cultivar during gelatinization process. The proposed
mati’ rice prepared in different rice cookers. Volatiles were identified by combination proved a powerful system for easy and rapid detection of a
SPME/GC–MS. A similar technique was again followed to determine the wide range of VACs in fragrant rice samples.
aroma profiles of scented and non-scented rice cultivars (Bryant & As discussed above, several researchers have concluded that this
McClung, 2011). The study of Bryant et al. (2006) reported a huge was one of the best inventions because it is simple, effective and en-
variation in the aroma profile of both aromatic and non-aromatic rice vironmentally friendly. Thus, as an extraction technique prior to GC
cultivars which may provide insight depth to the combination of aroma analyzes, SPME offers significant benefits in rice volatile aroma com-
compounds which contribute a distinct flavor to particular cultivar. pounds study (Grimm et al., 2001). The results obtained from SPME
Again in 2011, Bryant et al. (2011) used the SPME technique along with methods were often better in terms of both quantitative and qualitative
GC–MS to distinguish non-aromatic rice (O. sativa L.) kernels from than conventional extraction methods (Bryant et al., 2011). The SPME's
aromatic rice kernels and developed a single kernel analysis method for strategies were found simple applications ranging from the quantitative
detection of 2-AP in aromatic rice germplasm. use of particular chemicals at low ppb levels to the complete identifi-
A new powerful device cold-fiber SPME was developed by cation of volatile aroma compounds in rice samples (Bryant et al., 2011;
Ghiasvand et al. (2007) for easy and rapid screening of a wide range of Grimm et al., 2001; Mathure et al., 2011). Many publications in the
flavors in the headspace of fragrant rice samples. Another new appa- field of rice volatile aroma compounds have been published in more
ratus was designed by Zeng et al. (2007) using SPME for direct ex- than decades because of the sustainability of SPME methods. Re-
traction of flavor volatiles from rice during cooking and tested due to searchers in this sector are still realizing the advantages of SPME.

21
D.K. Verma and P.P. Srivastav Food Research International 130 (2020) 108924

Therefore, after a critical discussion of the findings in which SPME pressure without leaving the traces thereby producing pure extract.
methods were used for the rice aroma study, it can be concluded that This methodology is based upon the principle that a fluid (gas) above its
SPME is a potent extraction method for further analysis of the impact of critical point exhibits the solution properties of a liquid solvent. CO2 is
rice VACs in terms of accuracy. considered as the most suitable extractant because it has moderate
critical parameters viz. 7.38 MPa (74 bar) pressure and 31.04 °C tem-
6.1.3. Supercritical fluid extraction perature (Otto & Thomas, 1967). The extraction of VACs can also be
Supercritical fluid extraction (SFE) is one of the most innovative achieved using a static or dynamic method. A few examples of the
methods of solvent extraction for separation and extraction process of application of this method in rice aroma research found (Table 3) which
volatile/aromatic compounds by the use of supercritical fluids as the was carried out by Bhattacharjee et al. (2003) and Yahya (2011).
extraction solvent (Bhattacharjee et al., 2003; King, 2002; McHugh & In the experiments, the VACs of rice were isolated by extraction
Krukonis, 1986; Yahya, 2011). Supercritical fluids are a kind of clean with supercritical CO2 under pressure followed by atmospheric steam
solvent in the view of ‘Green Chemistry,’ less toxic than organic solvents distillation and enrichment of steam volatiles on Porapak Q. Although
have been considered as so as in this method. A widely used super- SFE is able to recover the majority of the VACs, it is also more selective,
critical fluid is carbon dioxide (CO2), sometimes modified by ethanol or and therefore less effective, than solvent extraction, i.e. fewer com-
methanol as such co-solvents (Zhang & Li, 2010). Therefore, Lou and pounds are extracted with SFE than with solvent extraction (King,
Chen (1996) found that SFE is an alternative to liquid extraction and 2002; McHugh & Krukonis, 1986). At present, SFE has been applied to
also reported that this is proved to be an efficient sample preparation the extraction of volatile/aromatic compounds from rice and other
method. Because of CO2 is quite simple to remove simply by reducing plant samples such as fruits, vegetables, spices and so on (Khaw, Parat,
pressure, leaving almost no trace, and is one of the greenhouse gases Shaw, & Falconer, 2017). Study of novel supercritical fluid and devel-
(King, 2002; McHugh & Krukonis, 1986). Therefore, the consequent opment of small scale SFE instrument are necessary for the further
treatment is simple when using SFE to the extraction of volatile/aro- application of SFE for extraction of VACs in the rice industry in the
matic compounds. future.
The SFE process involves the separation of one VAC (the extractant)
from another (the matrix) using supercritical fluids (CO2) as an ex- 6.2. Identification and quantification methods
tracting solvent. Fig. 4 represents the schematic diagram of the SFE
extraction unit which comprises of CO2 cylinder, and surge tank The identification and characterization of VACs from sample matrix
(stainless steel encased cylinder) having a thermostatic bath to control of various types of rice and rice products are still a big challenge for
the temperature. A high-pressure pump equipped with a manometer researchers and scientists, despite the availability of sophisticated
and a micrometric valve is essential to regulate the extraction pressure. methods for aroma analysis. VACs are usually presented in the various
The SFE assembly also contains the encased separators, collectors and sample matrix at a very low level of concentrations i.e. ppm or even ppb
gas measuring devices (Fig. 4). In SFE of botanicals, the CO2 is con- level which may contribute to flavors or off-flavors. These on-flavors or
sidered as the king of extraction solvents. The supercritical CO2 had a off-flavors are completely depended upon the presented levels of con-
critical temperature of 31 °C and critical pressure of 74 bar, thereby centration of the particular VACs. In order to aroma research of rice and
highly compressed gases which can possess the properties of liquids, as rice's products, our knowledge and scientific understanding are because
well as gases, are preferred. The supercritical fluids can run the reac- of the obtained results of the presence of different levels of its con-
tions which were otherwise impossible using conventional solvents. SFE centration.
is a quick technique where the process can finish within 10–60 min and In addition, it is also a fact and universally known that rice VACs
analyte can be separated from supercritical fluid by releasing the have seen a wide range of variations in their characteristics likewise

Fig. 4. Schematic diagram of Supercritical Fluid Extraction (SFE) set-up. (1) CO2 cylinder, (2) Surge tank, (3) Extraction, (4) & (5) Separators, (6) Collector and Gas
measuring device, (7) & (8) Thermostatic baths, and (9) Isocratic pump (Sarmento, Ferreira, & Hense, 2006).

22
Table 7
Summary of experimental condition different analytical methods employed for identification and quantification rice VACs.
(A) Experimental Conditions of GC–MS

References GC Conditions MS Conditions

Column Column Dimensions Injector Detector Oven Temperature Split Carrier Ion Source Electron Scan Range Interface Others
Types Temperature Temperature (°C) ratio Gas with temperature Energy Temperature
D.K. Verma and P.P. Srivastav

(°C) (°C) Flow (°C) (eV) (°C)


Rate

Bhattacharjee et al. DB-5 50 m × 0.3 mm × 0.25 µm 140 200 40 °C (for 5 min) – Helium, – 70 – – Electron
(2003) Capillary heated to 200 °C at 21 mL/ multiplier
Column 4 °C/min(for 5 min) min voltage: 1 kV
Boontakham et al. HP-5MS 30 m × 0.25 mm × 0.25 μm 230 – 45 °C heated to – Helium, 230 70 29–550 m/z – Electron
(2019) Capillary 230 °C at 2 °C/min 1 mL/min multiplier
Column (for 13 min) voltage: 1350 V
Bryant and McClung DB-5 30 m × 0.25 mm × 0.25 µm 260 – 50 °C (for 1 min) Splitless Helium, – – 40 to 650 m/ – –
(2011) Capillary heated to 260 °C at mode 1.0 mL/ z
Column 5 °C/min, to 260 °C min
(for 4 min)
Bryant et al. (2006, DB-5 30 m × 0.25 mm × 0.25 µm 270 – 50 °C (for 1 min) to Splitless Helium, 40–200 m/z
2011) Capillary 250 °C at 10 °C/min mode 40 cm/s
Column and
1.0 mL/
min
Cho and Kays (2013) Fused 30 m × 0.25 mm × 0.25 μm 225 – 40 °C (for 1 min), 0.5:1 Helium, 230 70 35–350 mass 280 Multiplier
Capillary heated to 65 °C at 1 mL/min units voltage: 1247 V
Column 1.5 °C/min (for

23
1 min), to 120 °C at
2 °C/min (for 1 min),
to 280 °C at 15 °C/
min (for 5 min)
Choi et al. (2019) DB-Wax 30 m × 0.25 mm × 0.25 μm 260 – 50 °C (for 1 min), Splitless Helium, 230 70 30–350 m/z 240 –
Capillary heated to 260 °C at mode 1 mL/min at 3.06
Column 5 °C/min (for 4-min) scans/s
Fenga et al. (2011)) HP- 60 m × 0.25 mm × 0.25 μm 250 – 60 °C for 1 min to 50:1 Helium, 230 70 20–450 m/z – Electron
INNOWAX 220 °C at 3 °C/min 1 mL/min multiplier:
Capillary (for 5 min) 1035 V
Column
Ghiasvand et al. SLB-5MS 10 m × 0.18 mm × 0.18 µm 250 – 40 °C to 250 °C at Helium, 220 70 35–450 m/z – –
(2007) Fused Silica 30 °C/min 1.0 mL/ at 50 scans/s
(Si) Capillary min
Column
Goufo et al. (2010) Fused Silica 30 m × 0.25 mm × 0.25 µm 250 – 40 °C (for 1 min) Splitless Helium, – 70 35–400. m/z 230 Electron
(Si) Capillary heated to 150 °C at mode 1.0 mL/ multiplier
Column 4 °C/min to 220 °C at min voltage: 1365 v
3 °C/min.
Hinge et al. (2016a, b) VF5-MS 30 m × 0.25 mm × 0.25 μm 260 – 45 °C (for 1 min) – Helium, 180 70 35 – 275 m/z 230 –
Capillary heated to 55 °C at 1 mL/min and
Column 5 °C/min to 120 °C at 20–400 m/z
9 °C/min to 240 °C at
15 °C/min (for 1 min)
Laohakunjit and Innowax 25 m × 0.2 mm × 0.4 μm 170 – 50 °C (for 2 min) – Helium, 230 – 50 to 400 m/ – Electron
Kerdchoechuen Capillary heated to 0.6 mL/ z multiplier
(2007) Column 170 °C at 7 °C /min min Voltage: 2600 V
(for 5 min)
(continued on next page)
Food Research International 130 (2020) 108924
Table 7 (continued)

(A) Experimental Conditions of GC–MS

References GC Conditions MS Conditions

Column Column Dimensions Injector Detector Oven Temperature Split Carrier Ion Source Electron Scan Range Interface Others
Types Temperature Temperature (°C) ratio Gas with temperature Energy Temperature
(°C) (°C) Flow (°C) (eV) (°C)
D.K. Verma and P.P. Srivastav

Rate

Lee et al. (2019) Rxi-5Sil MS 30 m × 0.25 mm – – 40 °C (for 5 min), – Helium, 200 70 35–220 m/z 270 –
Capillary heated to 160 °C at 1.0 mL/
Column 2.5 °C/min to 270 °C min
at 20 °C/min (for
5 min)
Lim et al. (2018) DB-5 30 m × 0.25 mm × 0.25 μm 270 – 40 °C increased to 1:2 Helium, 200 70 40–300 m/z 270 –
Capillary 100 °C at 5 °C/min 1 mL/min
Column for 3 min to 250 °C at
10 °C/min
Lin et al. (2010) Capillary 30 m × 0.25 mm × 0.25 μm – – 50 °C then heated to Non-split Helium, 230 70 35–350 280 –
Column 165 °C at 10 °C/min injection 1.0 mL/ amu.
(for 5 min) heated to min
250 °C at 15C/min,
(for 3 min)
Mahmud et al. (2018) Rxi-5Sil MS 30 m × 0.25 mm × 0.50 μm 250 – 40 °C (for 5 min) Splitless Helium, 200 70 35–650 m/z 270 –
Capillary heated to 160 °C at mode 1.4 mL/
Column 2.5 °C/min, to 270 °C min
at 20 °C/min (for
5 min)

24
Maraval et al. (2008) Fused Silica 0.32 mm × 30 m × 0.5 μm 240 – 40 to 240 °C at 6 °C/ 1:1 Helium, 230 70 29–350 m/z 260 –
(Si) Capillary min for 10 min. 1.5 mL/
Column min
Maraval et al. (2010) DB-Wax 30 m × 0.32 mm × 0.5 µm 250, 240 – 40 °C (for 3 min), Splitless Helium, 150, – 60–120 m/z 260 –
Fused Silica heated to 120 °C at mode 1 mL/min 230 and 29 to
(Si) Capillary 15 °C/min to 245 °C and 350 m/z
Column at 15 °C/min (for 1.5 mL/
10 min) min
Monsoor and Proctor CP-Sil8 and 30 m × 0.25 mm × 0.25 µm 270 – 50 °C (for 5 min) to – – 280 70 35 to – –
(2004) CB-MS Fused 200 °C at 5 °C/min 350 mg
Silica (Si) (for 1 min)
Capillary
Column
Park et al. (2010) DB-Wax 60 m × 0.25 mm × 0.25 µm 200 250 40 °C (for 5 min) – Helium, – 70 33–330 amu 280 electron
Capillary heated to 200 °C at 1.0 mL/ at scan rate multiplier
Column 2 °C/min to 200 °C min 4.76 scans/ voltage of
for 20 min sec 1,894 V
Peddamma et al. Fused Silica 30 m × 0.25 mm × 1.4 μm – – 40 °C for 2 min Splitless Helium, 230 – – – Quadrupole
(2018) (Si) Capillary heated to 240 °C at mode 1 mL/min temperatures:
Column 10 °C/min 150 °C
Tananuwong and HP-FFAP 25 m × 0.32 mm × 0.50 µm 200 – 45 °C to 80 °C at 2 °C/ – Helium, – 70 20–350 m/z 250 –
Lertsiri (2010) Capillary min to 120 °C at 4 °C/ 1.5 mL/
Column min to 230 °C at min
10 °C/min
(continued on next page)
Food Research International 130 (2020) 108924
Table 7 (continued)

(A) Experimental Conditions of GC–MS

References GC Conditions MS Conditions

Column Column Dimensions Injector Detector Oven Temperature Split Carrier Ion Source Electron Scan Range Interface Others
Types Temperature Temperature (°C) ratio Gas with temperature Energy Temperature
(°C) (°C) Flow (°C) (eV) (°C)
D.K. Verma and P.P. Srivastav

Rate

Wang and Ha (2012) HP-5 Fused 30 m × 0.25 mm × 0.25 µm 250 – 40 °C Splitless Helium, 230 – – 230 Quadrupole
Silica (Si) (held 4 min), mode 1.1 mL/ temperature:
Capillary increased to 120 °C at min 150
Column of 3 °C/min to 250 °C
at of 10 °C/min for
7 min
Yang et al. (2008a, b, Fused Silica 30 m × 0.25 mm × 0.25 µm 225 – 40 °C (for 1 min), 5:1 and Helium, 230 70 35–350 mass 280 Multiplier
2010) (Si) Capillary then heated to 65 °C 0.5:1 1.0 mL/ units voltage: 1247 V
Column (HP- (for 1 min), at 1.5 °C/ min and
5MS) min, to 120 °C (for 2.0 mL/
1 min) at 2 °C/min, min
and lastly at 15 °C/
min to 280 °C (for
5 min)
Zeng et al. (2007, DB-Wax 30 m × 0.25 mm × 0.25 µm 250 – 40 °C (for 2 min) – Helium, – 70 40–400. m/z 230 –
2008a, b, 2009) Capillary heated to 230 °C at 2.0 mL/
Column 4 °C/min (for min
4.5 min)

25
(B) Experimental Conditions of GC-FID

References Column Types Column Dimensions Injector Detector Oven Temperature (°C) Carrier Gas with
Temperature (°C) Temperature (°C) Flow Rate

Bergman et al. (2000) DB-5 Column 30m × 0.53mm 155 300 35 °C for 1 min at 9 °C/min to 120°C to Helium, 7.2 mL/
275 °C at 25°C/min for 2 min min
Borompichaichartkul et al. HP-5 Column – – 250 45 °C heated to 65 °C at 0.5 °C/min to 3mL/min
(2007) 250 °C
Bounphanousay et al. (2008) SPB-5 Column 35 μm × 250 μm × 0.25 μm – 300 35 °C heated to 70 °C for 1.79 min at 5 °C/ –
min to 100 °C at 10°C/min to 270 °C at
25 °C/min for 2 min
Goufo et al. (2011) HP-5 Fused Silica (Si) Capillary 60 m × 0.32 mm × 1.0 μm 230 250 50 °C increased to 200 °C at 5 °C/min Helium, 3 mL/
Column min
Grimm et al. (2011) DB-WAX Capillary Column 30 m × 0.25 mm 155 – 40 °C for 1 min then heated to 120 °C at Helium, 1.1 mL/
9 °C/min then at 25 °C/min to 250 °C for 5 min
min
Kaikavoosi et al. (2015) Capillary Column 30 m × 0.32 μm – – 50 °C (for 1 min) heated to 60 °C at 4 °C/ Nitrogen
min to 120 °C at 7 °C/min to 240 °C at
15 °C/min (for 1 min)
Kim et al. (2008b) DB5MS Column 30 m × 0.32 mm × 0.25 μm 155 300 40 °C for 1 min then heated to 120 °C at 9 Nitrogen, 1 mL/
rpm for 1 min and then at 25 °C. min
Laguerre et al. (2007) DB −5 60 m × 0.32 mm × 0.25 μm 250 – 40 °C for 45 min heated to 115 °C at 3 °C/ Helium, 1.9 mL/
Fused Silica (Si) Capillary Column min, to 220 °C for 5 min. min
Liyanaarachchi et al. (2014) SUPELCOWAXTM10 Fused Silica (Si) 30 m × 0.25 mm × 0.25 μm – – 40 °C heated to 225 °C at 10 °C/min (for Argon, 1 mL/min
Capillary Column 40 min)
Mathure et al. (2011) Capillary Column coupled with FID; 30 m × 0.32 μm – – 50 °C (for 1 min) heated to 100 °C at 4 °C/ –
min to 240 °C at 50 °C/min (of 2 min)
(continued on next page)
Food Research International 130 (2020) 108924
Table 7 (continued)

(B) Experimental Conditions of GC-FID

References Column Types Column Dimensions Injector Detector Oven Temperature (°C) Carrier Gas with
Temperature (°C) Temperature (°C) Flow Rate

Sriseadka et al. (2006) Fused Silica (Si) Capillary Column (DB- 15 m × 0.32 mm × 0.15 µm; 30 m 230 – 50 °C to 70 °C at a 1 °C/min to 125 °C at –
1701, DB-35MS, and HP-5) × 0.53 mm × 1.0 µm and 30m × 5 °C/min
D.K. Verma and P.P. Srivastav

0.53 mm × 1.5 µm
Wongpornchai et al. (2004) Fused Silica (Si) Capillary Column 30 m ×0.25 mm× 0.25 µm 250 – 45 °C to 120 °C at 5 °C/min for 15 min. Helium, 1 mL/
min
Yahya et al. (2011) Capillary Column coupled with FID 25.0m × 0.20mm × 0.40µm 170 250 50 °C for 1 min, heated to 170 °C at 7 °C/ Helium, 1.3 mL/
min (for 5 min) min

(C) Experimental Conditions of GC-O

References GC Conditions MS//FID/O Conditions

Column Type Column Injector Detector Oven Temperature (°C) Split Carrier Ion Source Electron Scan Range Interface Others
Dimensions Temperature Temperature ratio Gas with temperature Energy Temperature (°C)
(°C) Flow Rate (°C) (eV)

Boeswetter et al. DB-FFAP and 30 m × 0.32 – – 40 °C for 2 min, heated to 1:1 Helium – – – – –
(2019) DB-5 Fused mm × 0.25 μm 230 °C at 6 °C/min gas, 1.95
Silica (Si) (DB-FFAP column) or to mL/min
Capillary 240 °C (DB-5 column) for 5
Column min
Cho and Kays (2013) Fused 30 m × 0.25 225 – 40 °C (for 1 min), heated to 0.5:1 Helium, 230 70 35–350 mass 280 Multiplier
Capillary mm × 0.25 μm 65 °C at 1.5 °C/min (for 1 2.0 mL/ units voltage: 1247 V

26
Column min), to 120 °C at 2 °C/min min
(for 1 min), to 280 °C at
15 °C/min (for 5 min)
Mahattanatawee and Column 30 m × 0.32 220 275 40–240 °C at 7 °C/min – Helium The column effluent was split, 1/3rd of the flow was conducted to the FID and the other 2/
Rouseff (2014) mm × 0.5 μm gas, 2.0 3rds to the olfactory port for sniffing.
mL/min
Limpawattana et al. Fused Silica 30 m × 0.20 225 – 40 °C (for 1 min), then 0.5:1 Helium – 70 Volatiles exiting the column were split between the mass
(2008) (Si) Capillary mm × 0.25 µm heated to 65 °C (for 1 min), gas, 2.0 spectrometer for identification and quantification and the
Column at 1.5 °C/min, to 120 °C (for mL/min sniffing port with humidified purged air for description
1 min) at 2 °C/min, and and intensity assessment.
lastly at 15 °C/min to 280 °C
(for 5 min)
Maraval et al. (2008) Fused Silica 0.32 mm × 30 240 – 40–240 °C at 6 °C/min for 10 1:1 Helium – – – – –
(Si) Capillary m × 0.5 μm min. gas, 1.5
Column DB- mL/min
Wax
Yang et al. (2008a) Fused Silica 30 m × 0.25 – – – 0.5:1 Helium – – – – –
(Si) Capillary mm × 0.25 µm gas, 2.0
Column mL/min
Yang et al. (2008b) Fused Silica 30 m × 0.25 225 – 40 °C (for 1 min), then 0.5:1 Helium 230 70 280 35–350 mass units Multiplier
(Si) Capillary mm × 0.25 µm heated to 65 °C (for 1 min), gas, 2.0 voltage of 1247
Column at 1.5 °C/min, to 120 °C (for mL/min V
1 min) at 2 °C/min, and
lastly at 15 °C/min to 280 °C
(for 5 min)
Food Research International 130 (2020) 108924
D.K. Verma and P.P. Srivastav Food Research International 130 (2020) 108924

polarities, solubilities, volatilities, and thermal and pH stabilities (Zhou industrialized, etc. who are engaged with research on aroma and flavor.
et al., 1999). The sample matrix of rice and rice products contains an However, the excellency of the GC-FID over the other analytical method
array of VACs which may be very complex and cause interference with is subjected to the great consideration among the peoples of rice aroma
the isolation and extraction methods. Thus, on the basis of observations research because it enables the identification and quantification with
from available literature reports, it can be concluded that there is no the differentiation of a wide range of aroma- and flavor-active com-
single, simple method for the identification and characterization of pounds with their existing concentration levels from different in-
VACs (Withycombe et al., 1978). vestigate sample matrix of rice and rice products under the temperature
In this order, the instrumentation methods are recently evolved for of GC inlet (Zhang & Li, 2010). Identification of VACs of rice using GC-
identification and characterization of rice VACs as GC–MS, GC-FID, and FID is done by comparing the retention time (RT) and the retention
GC-O. These methods are receiving wide importance, attention and its times are further converted into the system-independent constant
application in the field of rice aroma research because they all are known as Kovats retention index (KRI). The values of KRI are of the
modern and recently developed, technologically very advanced normalized values of RT for adjacently eluting n-alkanes with those RT
(Table 7). These analytical methods are discussed in the following values obtained from chromatogram. The conditions of GC-FID like
section. column (type and dimension), temperature (injector, detector, and
oven), and flow rate of carrier gas, etc. which are highly influenced to
6.2.1. Gas chromatography-mass spectrometry the RT values. Some published works since its first report to till date are
Gas Chromatography-Mass Spectrometry (GC–MS) is a hyphenated examples of research on rice VACs which focussed and describe to the
analytical method in which two tools are combined with together, one success stories of GC-FID method (Grimm et al., 2011; Kaikavoosi, Kad,
is GC and another is MS to form a powerful instrumentation for analysis Zanan, & Nadaf, 2015; Mathure et al., 2011; Sunthonvit et al., 2005;
of VACs of different class from the sample matrix of various rice and Yahya, Fryer, & Bakalisa, 2011). Many research reports have already
Rice's products (Zhou et al., 1999). GC–MS has been proved to be very been published in this subject matter and some are summarised in
sensitive with respect to the qualitative and quantitative analysis of all Table 7(B).
known and unknown VACs of different classes which are normally
presented in sample matrix of rice and rice products in which GC per- 6.2.3. Gas chromatography–olfactometry
formed to determination and separation while identification and char- Gas chromatography–olfactometry (GC-O) is an analytical instru-
acterization of each individual atom compound from sample matrix by ment like the GC–MS and GC-FID method but one of the more advanced
MS (Kaseleht et al., 2011; Weber et al., 2000). The samples were and effective analytical method, which is being used for the identifi-
quantified by injecting into GC–MS for desorption at a certain opti- cation of impact VACs in sample matrix of rice. In 1964, GC-O was first
mized temperature with split or splitless mode. The VACs were iden- mentioned in the literature after the separation of volatiles in packed
tified by using a particular type if typical capillary column which may columns (Fuller, Steltenkamp, & Tisserand, 1964). In GC–O, impact
vary in their sizes like length, width, and thickness. MS performance on VACs are eluted from the chromatographic column by trained assessor
identification and characterization is based on an analysis of generated or group of assessors. This is perceived simultaneously with the help of
charged particle (ions) from molecules of the analyses. MS is used for two detectors i.e. MS or FID as a conventional detector and the second
fragmentation at electronic impact (EI) with a certain source of tem- one is human olfactory system depicted in Fig. 5 (Wardencki, Chmiel, &
perature and further transfer line at a certain temperature. The com- Dymerski, 2013). The human olfactory system means human nose as a
pounds are scanned at normal mode between particular mas units, in detector that has specific sensitivity with respect to the identification
the case of rice aroma study; it is seen between 50 and 500 mass units. capability of GC. Osme is a time-intensity of GC-O that directly involves
After this, Identification of the VACs of sample matrix is done by for estimation of the magnitude of intensity using human nose as ol-
comparing the mass spectra and retention time data with those sup- factory assessor and gives a verbal descriptor for each impact aroma
plemented by NIST GC–MS library or other libraries that are fabricated compound of rice (McDaniel, Miranda-Lopez, Watson, Michaels, &
during the installation of GC–MS. Generally, various types of MS de- Libbey, 1990).
tectors and introduced sampling methods enable application at a broad There are some literal advantages of GC-O application i.e. GC-O on a
spectrum for sample analysis. According to Gross (2004), there are sample enables work to be focused on parts of the chromatogram where
three specific regions for MS instrumentation; ionizer, ion analyzer, and compounds of greatest interest are suspected. And another is that GC-O
detector. This has made very easier to definite characterization of all particularly becomes more important when extracts obtained by solvent
the possible information with corresponding to the characteristics VACs extraction, especially ones from rice, can be very complex and the GC
of rice sample matrix than before. To date, the advance and improved chromatogram may contain many co-eluting compounds, which make
GC with their uses in different dimensional to provide the details re- identification of individual VACs difficult. One way to overcome this
garding their molecular weight and chemical structures of identified problem is to fractionate the extract, and hopefully move co-eluting
and quantified of complex array of VACs from sample matrix of various peaks into the different fractions for better identification.
types of rice and rice products, are of great importance. Many published As a result, the GC–O is applied to identify impact VACs not only an
research reports have been summarised in Table 7(A). instrumental but also a sensorial analysis (Delahunty, Eyres, & Dufour,
2006). Therefore, different methodologies have been developed which
6.2.2. Gas chromatography-flame ionization detector employed to design GC-O experiments include GC-O experiments, re-
Gas Chromatography-Flame Ionization Detector (GC-FID) is another cording the data and estimating the sensory contribution of individual
most powerful analytical method but comparatively, GC–MS has less VAC, etc. For instance, many studies with the successful application of
application in rice aroma research. In this analytical method, GC is GC–O with aroma extract dilution analysis (AEDA) and detection fre-
coupled with FID for the identification and quantification of VACs from quencies (DF) have been completed for rice aroma identification. Some
sample matrix of rice and rice products. In one aspect, a breakthrough of them are summarised in Table 7(C).
in rice aroma research was realized when GC-FID was introduced as
analytical method. While in another aspect, it was also a fact that 7. Concluding remarks
quantification of extracted amounts of the particular aroma compound
like 2-AP from sample matrix of rice by this analytical method is not The quality of rice is judged globally by its cooking properties,
enough. There is an extensive contemplation on this method require appearance, taste, odor, and aroma. Rice aroma is an important factor
because it capable of performance best so that GC-FID method could in deciding the pricing of rice in the International market. 2-AP – the
make its own identity and attention between the scientist, researchers, pop-corn like flavor varies among different cultivars of rice (1–10 ppb

27
D.K. Verma and P.P. Srivastav Food Research International 130 (2020) 108924

Fig. 5. Schematic diagram of GC-O system (Wardencki et al., 2013).

to 2 ppm) thus is signifying the difference between aromatic and non- Kumar Verma is highly thankful to Mamta Thakur (Department of Food
aromatic rice cultivars. Till today, i.e. 2019 from 1980s more than 500 Engineering and Technology, Sant Longowal Institute of Engineering
VACs had been identified in rice and rice products. Besides 2-AP, and Technology, Punjab, India) who have made my tasks as an author
mixture of aldehydes, ketones, organic acids, alcohols, nitrogen, and easier and pleasure by their consistent support, cooperation and timely
sulfur are responsible to cause variety of flavors such as spicy-like, suggestion on technical corrections of the manuscript.
fruity-like, glue-like, bran-like, plastic-like, etc. However, 2-AP and
indole have been prioritized globally as factors to evaluate the aroma of Declaration of Competing Interest
rice varieties. Hexanal had been reported to cause oxidative rancidity in
rice. Sometimes structural breakdown also imparts off-flavor to rice and The authors declare that there is no conflict of interest.
rice products. Moreover, rice aroma must be extracted, identified and
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