2. Origins of Volatile Compounds in Pulses
2.1. Oxidation of Unsaturated Free Fatty Acids
Different classes of volatiles, such as aromatic hydrocarbons, aldehydes, alcohols, alkanes, ketones (furans) and esters, are mostly derived from enzymatic or nonenzymatic oxidation (autoxidation) of free fatty acids. Although pulses have a low fat content (0.8–7% of seed weight), this mechanism is dominant and strongly contributes to unpleasant odours, such as herbal, green, pea, beany, mould, and rancid notes
[10]. The synthesis of these compounds follows three phases.
2.2. Degradation of Free Amino Acids
The degradation of amino acids has been shown to be the second source of volatile compound production in pulses. Several origins exist, such as biodegradation in seeds, degradation by microorganisms, and Maillard reactions.
2.3. Degradation of Carotenoids
Terpenes can be derived from the degradation of carotenoids. Carotenoids are oxidized by LOX 2 at neutral pH and produce these volatile compounds
[11]. This origin is highly disputed. Indeed, due to the low concentrations found in plants, these molecules would be absorbed by plant roots at the soil level during their cultivation and then accumulate in the seeds
[12].
3. Extraction, Separation, Identification, and Semi-Quantification Methods
The characteristics of the studied pulses (cultivar and year and location of cultivation), conditions of storage, transformation, and volatile compound analysis are described in
Table 1 [13][14][15][16][17][18][19][20]. Different classical methods are used to extract volatile compounds, which are briefly described here. By using HS-SPME (HeadSpace Solid-Phase MicroExtraction), the volatile compounds in the vapour phase are first adsorbed on a fibre and desorbed in the GC (Gas Chromatography) injector to be separated and identified. This method is robust, rapid, simple to use, and solvent-free but allows only semi-quantification due to competition between analytes on the fibre
[21][22][23]. SAFE (Solvent-Assisted Flavour Evaporation) combines vacuum distillation and solvent extraction
[24]. This method allows quantification by a standard but requires a long extraction time and requires the use of organic solvents to extract volatiles
[23]. The differences highlighted in these two methods could also explain some differences between pulse volatile compounds.
Table 1. Characteristics of pulses: extraction and identification methods of volatile compounds.
Code |
Pulses |
Cultivar |
Year |
Location |
Storage |
Seed Transformation |
Extraction |
Separation and Identification |
References |
Black bean |
Black bean (Phaseolus vulgaris L.) |
AC Harblack |
2005 |
Morden, Canada |
Dry room (23 °C, 15–20% RH) (whole). |
Ground in flour (coffee mill) (whole). |
HS-SPME: 10 g in a 125-mL Erlenmeyer flask capped, DVB/CAR/PDMS Stable Flex SPME fibre at 50 °C for 1 h. |
GC-MS: desorption at 250 °C for 2 min, Supelcowax 10 polar column, started at 40/1/70 °C, then 70/5/200 °C and 200/50/250 °C. |
[25] |
CDC Rio |
Onyx |
Pinto bean |
Pinto bean (Phaseolus vulgaris L.) |
AC Pintoba |
Maverick |
Dark red kidney bean |
Dark red kidney bean (Phaseolus vulgaris L.) |
ROG 802 |
Redhawk |
Whole pea |
Pea (Pisum sativum L.) |
Eclipse (Yellow field pea) |
2005 |
Near Saskatoon, Canada |
4 °C (whole). |
Ground in flour (whole). |
HS-SPME: 3 g, CAR/PDMS SPME Fibre at 50 °C for 30 min. |
GC-MS: desorption at 300 °C for 3 min, VF-5MS capillary column, started at 35/6/80 °C and 80/20/280 °C. |
[26] |
2006 |
2007 |
Dehulled pea |
- |
Before 2013 |
- |
In a glass bottle, −18 °C. |
Ground in flour (dehulled). |
SAFE: 20 g in 100 mL of water, 2 h at 30 °C and 10–2 mbar. Liquid-liquid separation with 3 × 10 mL of CH2Cl2. Concentration using Kuderna Danish apparatus, 70 °C. |
GC-MS: ZB1.MS non-polar column, injection of 2 µL, started at 50/4/160 °C, then 160/15/320 °C. |
[27] |
Pea protein |
Protein isolate, Nutralys® (dehulled, wet process). |
- |
Before 2020 |
- |
- |
Protein concentrate (dehulled, dry process). |
HS-SPME: 1.5 g was dissolved into saturated NaCl solution for 1 h at 20 °C, then transferred into a bottle and incubated at 50 °C in an ultrasonic bath, insertion of the DVB/CAR/PDMS Stable Flex SPME fibre at 50 °C for 20 min. |
GC-MS: desorption at 250 °C for 3 min, DB-5MS column, started at 40/5/70 °C, then 70/10/200 °C and 200/50/250 °C. |
[28] |
Chickpea |
Chickpea (Cicer arietinum) |
Kabuli (Benying-1) |
2018 |
Urumqi, China |
−18 °C for a maximum of 3 weeks (whole). −20 °C for a maximum of 1 week (powder). |
Dried using sunlight before storage (whole). Ground to a fine powder (80 mesh, mill). |
HS-SPME: 1.5 g was dispersed in water and 5 mL was placed in a 20-mL headspace sampling vial and capped, PDMS/DVB fibre at 60 °C for 60 min. |
GC-MS: desorption at 250 °C for 5 min, PEG 20 M column, started at 35/5/130 °C and 130/9/200 °C. |
[29] |
Desi (YZ-364) |
Faba bean Tannin |
Faba bean (Vicia faba L. minor) |
High tannin |
2016 |
Alberta, Canada |
In freezer bags (polypropylene), 22 °C and 18% RH in a dark and solvent-free room (flour). |
Ground in flour (impact mill) (whole). |
HS-SPME: 2 g was pre-incubated at 50 °C for 5 min, DVB/CAR/PDMS Stable Flex SPME fibre at 50 °C for 1 h. |
GC-MS: desorption at 250 °C for 60 s, DB-17 mod polarity column, 40/5/200 °C. |
[30] |
Low tannin |
Faba bean Location |
Low tannin (13 cultivars) |
2009 |
Barrhead, Canada |
- |
Ground in flour (coffee mill) (whole). |
HS-SPME: 10 g in a 125-mL Erlenmeyer flask capped, DVB/CAR/PDMS Stable Flex SPME fibre at 50 °C for 1 h. |
GC-MS: desorption at 250 °C for 2 min, Supelcowax 10 polar column, started at 40/1/70 °C, then 70/5/200 °C and 200/50/250 °C. |
[31] |
Namao, Canada |
Faba bean Storage |
High tannin |
2016 |
Alberta, Canada |
No storage. |
Ground in flour (micro-mill) with a water-cooled system to protect from overheating (whole). |
HS-SPME: 2 g was pre-incubated at 50 °C for 5 min, DVB/CAR/PDMS Stable Flex SPME fibre at 50 °C for 1 h. |
GC-MS: desorption at 250 °C for 60 s, DB-17 mod polarity column, 40/5/200 °C. |
[32] |
In bags (PE), in a dark and solvent-free room, 60 days (flour). |
22 °C, 19% RH. |
4 °C, 9% RH. |
−21 °C. |
RH, relative humidity; SAFE, Solvent-Assisted Flavour Evaporation; HS-SPME, HeadSpace Solid-Phase MicroExtraction; PE, polyethylene.
4. Identification and Quantification of Volatile Compounds in Pulses
In
Table 2,
Table 3,
Table 4,
Table 5,
Table 6 Table 7,
Table 8,
Table 9,
Table 10,
Table 11,
Table 12 and
Table 13, each table describes a chemical class of volatile compounds: aromatic hydrocarbons, aldehydes, alkanes/alkenes, alcohols, ketones, acids, esters (without lactones), pyrazines, terpenes, furans, lactones, and other volatile compounds. For each pulse, one column corresponds to the minimum and the maximum (min–max) of a set of different cultivars, harvest years, locations and conditions of storage, or seed transformations (dehulling and production of protein concentrates or isolates) (see
Table 2 for more details).
Table 2. Aromatic hydrocarbons in pulses (expressed as percentages).
Aromatic Hydrocarbons |
CAS |
Origin (s) |
Black Bean |
Pinto Bean |
Dark Red Kidney Bean |
Pea |
Chickpea |
Faba Bean |
Whole |
Dehulled |
Tannin |
Location |
Storage |
26], and “Dehulled” corresponds to dehulled pea flour
[27]. “Chickpea” refers to 2 cultivars
[29]. For faba beans, “Tannin” corresponds to a group of low-tannin cultivars and a group of high-tannin cultivars
[30], “Location” corresponds to different low-tannin cultivars that were harvested at 2 different locations in Canada
[31], and “Storage” corresponds to high-tannin cultivars that were stored under 3 different conditions (ambient, positive, and negative temperatures) for 60 days and a control (sample stored for 0 days)
[32]. No aromatic hydrocarbon was detected in pea proteins (concentrate and isolate) (see
Table 1 for more details).
Table 3. Aldehydes in pulses (expressed as percentages).
Aldehydes |
CAS |
Origin (s) |
Black Bean |
Pinto Bean |
Dark Red Kidney Bean |
Pea |
, and “Protein” refers to protein concentrate (dry process)
[28] and to protein isolate (wet process)
[27]. “Chickpea” refers to 2 cultivars
[29]. For faba beans, “Tannin” corresponds to a group of low-tannin cultivars and a group of high-tannin cultivars
[30], and “Storage” corresponds to high-tannin cultivars that were stored under 3 different conditions (ambient, positive, and negative temperatures) during 60 days and a control (sample stored for 0 days)
[32]. No ester was detected in “location” faba beans (see
Table 1 for more details).
Table 9. Pyrazines in pulses (expressed as percentages).
Pyrazines | Chickpea |
CAS | Faba Bean |
Origin (s) |
Pea |
Whole |
Dehulled |
Whole | Proteins |
Dehulled |
Protein |
|
|
|
31], and “Storage” corresponds to high-tannin cultivars that were stored under 3 different conditions (ambient, positive, and negative temperatures) for 60 days and a control (sample stored for 0 days)
[32]. No furan was detected in chickpeas (see
Table 1 for more details).
Table 12. Lactones in pulses (expressed as percentages).
Lactones |
CAS |
Origin (s) |
Pea |
Chickpea |
Faba Bean |
Tannin |
2,3-Diethyl-5-methylpyrazine |
18138-04-0 |
|
0.00–1.30 |
|
|
28] and protein isolate (wet process)
[27]. “Chickpea” refers to 2 cultivars
[29]. For faba beans, “Tannin” corresponds to a group of low-tannin cultivars and a group of high-tannin cultivars
[30], and “Storage” corresponds to high-tannin cultivars that were stored under 3 different conditions (ambient, positive, and negative temperatures) during 60 days and a control (sample stored for 0 days)
[32]. No lactone was detected in black beans, pinto beans, dark red kidney beans, whole peas, and “location” faba beans (see
Table 1 for more details).
Table 13. Other volatiles in pulses (expressed as percentages).
Other Volatiles |
CAS |
Black Bean |
Pinto Bean |
Dark Red Kidney Bean |
Pea |
Chickpea |
Faba Bean |
Location |
Dehulled | Storage |
Proteins |
Tannin |
Storage |
Whole |
Dehulled |
Proteins |
Tannin |
Storage |
Toluene |
108-88-3 |
FFA 1,2 |
0.00–0.86 |
0.96–1.86 |
0.00–0.73 |
1.20–2.40 |
Coelution |
γ-Butyrolactone |
96-48-0 |
|
|
|
0.00–0.85 |
0.32–0.63 |
0.22–1.08 | |
0.26–0.37 |
0.88–0.96 |
0.41–3.12 |
m-Ethyltoluene |
620-14-4 | |
|
0.00–0.50 |
|
Benzaldehyde |
100-52-7 |
FFA 2; AA 5,7,11 |
2.36–3.64 |
2.58–2.60 |
3.46–4.04 |
|
|
0.00–2.11 |
0.00–2.19 |
0.36–0.45 |
2.09–2.10 |
Estragole | 0.46–0.85 |
140-67-0 |
|
|
|
|
|
|
|
|
0.00–0.16 |
|
|
|
4-Ethylbenzaldehyde | |
53951-50-1 |
|
|
| |
|
|
|
|
0.09–0.11 |
2-Ethylhexyl ethanoate |
0.00–0.28 |
0.00–0.54 |
|
|
|
|
103-09-3 |
|
|
|
|
|
2-Methyoxy-3-isopropyl(5or6)-methylpyrazine |
32021-41-3 |
AA 1 |
|
2.62 |
0.00–0.13 | |
|
|
|
0.00–0.79 |
3-Methylbutyrolactone |
1676-49-8 |
Benzene |
71-43-2 |
FFA 4 |
|
|
0.09–0.11 |
|
Phenylacetaldehyde |
122-78-1 |
AA 3,5,7,11 |
|
|
| |
|
|
0.00–0.67 |
|
0.14–0.17 |
|
0.21–0.39 |
Ethylbenzene |
100-41-4 |
FFA 1,2 |
0.00–0.45 |
0.00–0.44 |
|
0.30–0.80 |
|
|
0.12–0.17 |
1.19–1.28 |
Vanillin | 0.19–0.73 |
121-33-5 |
|
|
|
|
|
0.16 |
0.00–0.08 |
|
|
|
|
1,2,3-Trimethylbenzene |
526-73-8 |
FFA 2 |
0.00–0.54 |
0.54–1.03 |
|
|
|
|
2-Methylpropanal |
78-84-2 |
AA | 0.12–0.13 |
|
|
|
2-Methylbutanal |
96-17-3 |
AA 5,8,11 |
|
|
|
|
|
0.03–0.49 |
|
0.31–0.48 |
|
0.00–0.13 |
3-Methylbutanal |
590-86-3 |
AA 5,7,11 |
|
|
|
0.00–1.00 |
|
0.00–0.10 |
|
1.04–1.17 |
|
0.36–0.59 |
Pentanal |
110-62-3 |
FFA 2,9,10 |
0.00–0.59 |
0.60–0.79 |
Total |
|
|
24.42–28.01 |
18.19–23.57 |
25.77–33.33 |
10.70–17.70 |
3.02 |
40.21–63.66 |
12.41–12.91 |
29.14–36.39 |
58.05–60.58 |
9.19–79.03 |
1 [26];
2 [25];
3 [27];
4 [28];
5 [30];
6 [31];
7 [32];
8 [35];
9 [12];
10 [33][34];
11 [36]. FFA, free fatty acids; AA, amino acids. The value “min–max” corresponds to the minimum and maximum percentages for each volatile compound identified. “Black bean” refers to the 3 cultivars studied, and “Pinto bean” and “Dark red kidney bean” correspond to 2 cultivars for each
[25]. For peas, “Whole” corresponds to 3 different harvest years of the cultivar Eclipse (2005, 2006, and 2007)
[26], “Dehulled” corresponds to dehulled pea flour
[27], and “Protein” refers to protein concentrate (dry process)
[28] and protein isolate (wet process)
[27]. “Chickpea” refers to 2 cultivars
[29]. For faba beans, “Tannin” corresponds to a group of low-tannin cultivars and a group of high-tannin cultivars
[30], “Location” corresponds to different low-tannin cultivars that were harvested at 2 different locations in Canada
[31], and “Storage” corresponds to high-tannin cultivars that were stored under 3 different conditions (ambient, positive, and negative temperatures) for 60 days and a control (sample stored for 0 days)
[32] (see
Table 1 for more details).
Table 4. Alkanes/alkenes in pulses (expressed as percentages).
Alkanes/Alkenes |
CAS |
Origin (s) |
Black Bean |
Pinto Bean |
Dark Red Kidney Bean |
Pea |
Chickpea |
Faba Bean |
Whole |
Dehulled |
Proteins |
Tannin |
Location |
Storage |
Trichloromethane |
67-66-3 |
N 1 |
|
|
|
0.00–0.50 |
|
|
|
|
|
|
Octylcyclopropane |
1472-09-9 |
|
0.00–0.96 |
0.00–1.28 |
0.00–2.04 |
|
|
|
|
|
|
|
Pentane |
109-66-0 |
FFA 4 |
AA |
|
|
|
|
|
|
0.10–0.10 |
|
|
2,3,4 |
0.42 |
0.00–0.41 |
|
8.79–12.37 |
2.55–10.36 |
Butyl ethanoate |
123-86-4 |
|
|
|
|
|
|
|
|
|
0.00–0.25 |
Hexane |
110-54-3 |
FFA 4 |
0.74–1.54 |
1.14–1.72 |
0.83–0.86 |
|
|
|
|
Pentanoic acid |
109-52-4 |
|
0.48 |
|
|
|
11 | |
0.00–0.21 |
|
|
|
0.00–1.91 |
0.07–0.08 |
0.37–0.42 |
|
1 [26];
2 [25];
3 [31];
4 [33][34]. N, naturally present (not considered as a contaminant); FFA, free fatty acids. The value “min–max” corresponds to the minimum and maximum percentages for each volatile compound identified. “Black bean” refers to the 3 cultivars studied, and “Pinto bean” and “Dark red kidney bean” correspond to 2 cultivars for each
[25]. For peas, “Whole” corresponds to 3 different harvest years of the cultivar Eclipse (2005, 2006, and 2007)
[26], “Dehulled” corresponds to dehulled pea flour
[27], and “Protein” refers to protein concentrate (dry process)
[28] and protein isolate (wet process)
[27]. “Chickpea” refers to 2 cultivars
[29]. For faba beans, “Tannin” corresponds to a group of low-tannin cultivars and a group of high-tannin cultivars
[30], “Location” corresponds to different low-tannin cultivars that were harvested at 2 different locations in Canada
[31], and “Storage” corresponds to high-tannin cultivars that were stored under 3 different conditions (ambient, positive, and negative temperatures) for 60 days and a control (sample stored for 0 days)
[32] (see
Table 1 for more details).
Table 5. Alcohols in pulses (expressed as percentages).
Alcohols |
CAS |
Origin (s) |
Black Bean |
Pinto Bean |
Dark Red Kidney Bean |
Pea |
Chickpea |
Faba Bean |
Whole |
Dehulled |
Proteins |
Tannin |
Location |
Storage |
Ethanol |
64-17-5 |
AA 5 FFA 9,10,11 |
|
|
|
|
|
|
|
0.48–1.29 |
|
0.00–0.42 |
2-Phenylethanol |
60-12-8 |
|
|
|
[12]. CAR, carotenoids. The value “min–max” corresponds to the minimum and maximum percentages for each volatile compound identified. “Black bean” refers to the 3 cultivars studied, and “Pinto bean” and “Dark red kidney bean” correspond to 2 cultivars for each
[25]. For peas, “Whole” corresponds to 3 different harvest years of the cultivar Eclipse (2005, 2006, and 2007)
[26], “Dehulled” corresponds to dehulled pea flour
[27], and “Protein” refers to protein concentrate (dry process)
[28] and protein isolate (wet process)
[27]. For faba beans, “Tannin” corresponds to a group of low-tannin cultivars and a group of high-tannin cultivars
[30], and “Storage” corresponds to high-tannin cultivars that were stored under 3 different conditions (ambient, positive, and negative temperatures) during 60 days and a control (sample stored for 0 days)
[32]. No terpene was detected in chickpeas and “location” faba beans (see
Table 1 for more details).
Table 11. Furans in pulses (expressed as percentages).
Furans |
CAS |
Origin (s) |
Black Bean |
Pinto Bean |
Dark Red Kidney Bean |
Pea |
Faba Bean |
Whole |
Dehulled |
Proteins |
Tannin |
Location |
Storage |
AA | 5,7,11 |
|
|
|
|
0.45 |
|
|
|
|
0.27–0.34 |
|
0.00–0.83 |
2-Methoxy-3-isobutylpyrazine |
24683-00-9 |
AA 2 |
|
Trace |
|
|
|
Hexyl ethanoate |
142-92-7 |
FFA 2 |
|
|
Total |
| |
| |
|
|
|
|
|
0.00–1.30 |
2.62 |
0.00–0.13 | |
0.00–2.96 |
Hexanoic acid |
142-62-1 |
FFA 1 |
0.73 |
0.00−Coelution |
1.06–1.98 |
0.57–1.54 |
|
1 [27];
2 [37]. AA, amino acids. The value “min–max” corresponds to the minimum and maximum percentages for each volatile compound identified. For peas, “Whole” corresponds to 3 different harvest years of the cultivar Eclipse (2005, 2006, and 2007)
[26], “Dehulled” corresponds to dehulled pea flour
[27], and “Protein” refers to protein concentrate (dry process)
[28] and protein isolate (wet process)
[27]. No pyrazine was detected in black beans, pinto beans, dark red kidney beans, chickpeas, and faba beans (“tannin”, “location”, and “storage”) (see
Table 1 for more details.).
Table 10. Terpenes in pulses (expressed as percentages).
Terpenes |
CAS |
Origin (s) |
Black Bean |
Pinto Bean |
Dark Red Kidney Bean |
Pea |
Faba Bean |
Whole |
Dehulled |
Proteins |
Tannin |
Storage |
α-Pinene |
80-56-8 |
CAR 1,2 |
1.37–2.29 |
2.11–3.92 |
0.75–1.07 |
|
2-Methylfuran |
534-22-5 | |
|
|
|
FFA | 3 |
|
|
|
0.00–1.80 |
|
|
|
|
|
Δ3-Carene |
13466-78-9 |
CAR |
2-Ethylfuran | 1,2 |
0.00–0.50 |
0.00–0.48 |
3208-16-0 |
FFA |
0.30–0.70 |
|
|
|
|
1,5 |
0.00–0.64 |
0.62–0.74 |
0.00–0.58 |
0.00–3.90 |
|
|
|
|
Benzothiazole |
95-16-9 |
|
|
|
|
0.42 |
0.00–1.50 |
0.00–0.30 |
|
|
2-Butoxyethanol |
111-76-2 |
|
|
|
|
|
0.95 |
0.00–0.88 |
|
|
|
Limonene |
138-86-3 |
CAR |
1,2 |
0.00–1.36 |
1.31–2.96 |
4-Methyl-4-vinylbutyrolactone |
1073-11-6 |
|
|
|
|
0.08–0.09 |
|
4,5-Dimethylimidazole |
2302-39-8 |
|
|
| |
|
|
|
0.00–1.22 |
|
|
Pentolactone |
599-04-2 |
|
|
|
2.20–2.30 |
3-Methylhexane |
589-34-4 |
|
|
|
|
0.49–0.51 |
|
|
|
Ethyl cyanoacetate |
105-56-6 |
|
|
|
|
|
|
|
0.00–0.39 |
|
|
2-Ethyl hexanoic acid |
149-57-5 |
|
0.51 |
0.00–0.43 |
|
|
|
|
0.66 |
0.00–0.11 |
0.96 |
0.00–10.81 |
γ-Terpinene |
99-85-4 |
|
|
|
1,3,5-Trimethylbenzene |
|
|
|
|
0.00–0.79 |
|
|
0.00–2.50 |
|
|
|
|
Terpinolene |
586-62-9 |
|
|
|
|
|
|
|
|
0.00–0.12 |
|
3-Methylthiopropanal108-67-8 |
3268-49-3FFA 2 |
0.00–0.77 |
0.81–1.84 |
|
|
|
|
|
|
AA 0.00–0.19 |
3,11 |
|
Butylcyclohexane |
1678-93-9 |
| |
|
|
0.00–0.49 |
0.00–0.51 |
|
Decyl bromoacetate |
5436-93-1 |
|
|
|
|
|
|
|
0.00–0.36 |
0.00–0.32 |
0.00–0.34 |
|
|
|
|
|
|
Propylbenzene |
103-65-1 |
|
0.00–0.35 |
0.00–0.40 |
|
|
Heptanoic acid |
111-14-8 |
|
1.46 |
|
|
|
1,2-Dihydro-2-naphtalenylacetate | |
|
|
|
0.00–0.19 |
0.00–0.03 |
| |
- |
|
|
|
|
|
|
Cumene |
Heptane | |
0.80–1.06 |
|
|
Octanoic acid |
124-07-2 |
N 1; FFA 3 |
1.54 |
0.00−Coelution |
|
|
0.00–0.24 |
Ethyl propanoate |
105-37-3 |
|
|
|
|
|
Coelution |
0.00–17.19 |
|
|
|
Nonanoic acid |
112-05-0 |
FFA 3 |
1.92 |
0.00–1.40 |
|
|
0.00–0.58 |
108-94-1 |
|
Octyl pivalate |
Decanoic acid |
334-48-5 |
|
|
|
0.00–0.89 |
|
|
|
|
|
|
|
0.00–0.15 |
|
|
|
|
Palmitic acid |
57-10-3 |
|
|
|
12.00–15.00 |
|
|
5-Hexen-2-one |
109-49-9 |
|
|
|
|
|
3.29 |
0.00–1.75 |
|
|
|
|
Oleic acid |
112-80-1 |
|
|
|
11.00–24.00 |
|
|
Total |
|
|
7.07 |
0.63–1.84 |
32.77–40.16 |
11.33–16.39 |
3.24–13.15 |
1 [27];
2 [30];
3 [32];
4 [36]. AA, amino acids; N, naturally present (not considered as a contaminant); FFA, free fatty acids. The value “min–max” corresponds to the minimum and maximum percentages for each volatile compound identified. For peas, “Dehulled” corresponds to dehulled pea flour
[27], and “Protein” refers to protein concentrate (dry process)
[28] and protein isolate (wet process)
[27]. “Chickpea” refers to 2 cultivars
[29]. For faba beans, “Tannin” corresponds to a group of low-tannin cultivars and a group of high-tannin cultivars
[30], and “Storage” corresponds to high-tannin cultivars that were stored under 3 different conditions (ambient, positive, and negative temperatures) for 60 days and a control (sample stored for 0 days)
[32]. No acid was detected in black beans, pinto beans, red kidney beans, whole peas, and “location” faba beans (see
Table 1 for more details).
Table 8. Esters in pulses (expressed as percentages).
Esters |
CAS |
Origin (s) |
Black bean |
Pinto Bean |
Dark Red Kidney Bean |
Pea |
Chickpea |
Faba Bean |
Whole |
Dehulled |
Proteins |
Tannin |
Storage |
Ethyl ethanoate |
141-78-6 |
FFA 3 |
|
|
|
0.00–1.20 |
|
|
|
|
Thujospsene-I3 |
Dimethyl sulphide |
75-18-3 |
|
|
|
0.86–3.30 |
|
|
|
|
|
γ-Pentalactone |
108-29-2 |
|
1.01 |
|
|
|
|
Dimethyl disulphide |
624-92-0 |
|
|
|
0.00–0.80 |
|
- |
|
|
|
- |
|
|
|
|
|
|
|
|
|
0.00–0.76 |
|
|
Hexyl 2-methylbutanoate |
10032-15-2 |
|
|
|
|
|
|
|
|
|
0.00–3.54 |
Ethyl butanoate |
105-54-4 |
|
|
|
|
|
0.93 |
0.00–0.05 |
|
|
0.00–3.66 |
2-Ethylhexyl butanoate |
25415-84-3 |
|
|
|
|
|
|
|
|
|
0.00–0.92 |
6-Methyl-5-hepten-2-one |
110-93-0 |
FFA 2 |
Methyl isovalerate |
556-24-1 | ; CAR 4 |
1.97–2.45 |
0.94–1.76 |
1.27–2.44 |
|
|
|
0.82–0.87 |
1.08–1.50 |
1.06–1.09 |
0.00–1.27 |
|
|
|
|
δ-Caprolactone |
823-22-3 |
N 2 |
|
|
|
0.24–0.26 |
0.00–0.82 |
3-Phenylindole |
1504-16-1 |
0.00–0.84 |
0.49–1.18 |
0.72–0.73 |
|
|
|
|
|
|
142-82-5 |
FFA 3 |
0.54–1.15 |
0.94–1.07 |
0.57–0.76 |
|
|
|
|
|
0.55–0.56 |
|
98-82-8 |
Octane | FFA | 2 |
111-65-90.70–1.13 |
0.84–0.86 |
1.11–1.69 |
0.30–0.60 |
|
|
|
0.42–0.46 |
|
FFA | 4 |
1.74–2.66 |
0.00–1.74 |
1.89–3.64 |
|
|
|
|
|
1.79–1.96 |
|
p-Xylene |
106-42-3 |
FFA 1 |
1.15–1.50 |
0.00–1.20 |
0.00–1.17 |
0.40–1.00 |
|
|
|
0.27–0.38 |
0.00–0.70 |
1.03–1.11 |
|
|
0.00–0.73 |
|
|
2,6-Dimethyloctane |
2051-30-1 |
|
|
|
|
0.00–0.96 |
|
|
0.37–0.41 |
|
(E,E)-3,5-Octadien-2-ol |
69668-82-2 |
|
|
|
|
|
|
|
|
0.10–0.14 |
|
|
Nonanol |
143-08-8 |
FFA 7 |
0.42–1.30 |
0.92–1.10 |
0.00–0.43 |
|
1.27 |
0.00–2.69 |
|
0.92–1.14 |
0.28–0.41 |
0.85–1.74 |
Decanol |
112-30-1 |
|
|
|
|
|
|
|
|
0.22–0.29 |
|
|
Undecanol |
112-42-5 |
|
|
|
|
|
6.18 |
|
|
|
|
0.00–0.09 |
2-Pentadecyn-1-ol |
2834-00-6 |
|
|
|
|
|
|
|
0.00–0.55 |
|
|
|
Total |
|
|
6.13–7.72 |
8.05–9.04 |
4.67–7.41 |
7.40–12.70 |
36.33 |
8.22–30.70 |
11.22–13.01 |
24.21–27.63 |
13.00–13.27 |
4.34–53.01 |
1 [26];
2 [25];
3 [27];
4 [28];
5 [30];
6 [31];
7 [32];
8 [35];
9 [12];
10 [33][34];
11 [36]. AA, amino acids; FFA, free fatty acids. The value “min–max” corresponds to the minimum and maximum percentages for each volatile compound identified. “Black bean” refers to the 3 cultivars studied, and “Pinto bean” and “Dark red kidney bean” correspond to 2 cultivars for each
[25]. For peas, “Whole” corresponds to 3 different harvest years of the cultivar Eclipse (2005, 2006, and 2007)
[26], “Dehulled” corresponds to dehulled pea flour
[27], and “Protein” refers to protein concentrate (dry process)
[28] and protein isolate (wet process)
[27]. “Chickpea” refers to 2 cultivars
[29]. For faba beans, “Tannin” corresponds to a group of low-tannin cultivars and a group of high-tannin cultivars
[30], “Location” corresponds to different low-tannin cultivars that were harvested at 2 different locations in Canada
[31], and “Storage” corresponds to high-tannin cultivars that were stored under 3 different conditions (ambient, positive, and negative temperatures) for 60 days and a control (sample stored for 0 days)
[32] (see
Table 1 for more details).
Table 6. Ketones in pulses (expressed as percentages).
Ketones |
CAS |
Origin (s) |
Black Bean |
Pinto Bean |
Dark Red Kidney Bean |
Pea |
Chickpea |
Faba Bean |
Whole |
Dehulled |
Proteins |
Tannin |
Location |
Storage |
Acetophenone |
98-86-2 |
AA 5; FFA 6 |
0.63–0.98 |
0.53–0.77 |
0.00–0.82 |
|
|
|
|
0.33–0.36 |
|
0.00–0.50 |
p-Isopropylacetophenone |
645-13–6 |
|
|
|
|
|
|
0.00–0.73 |
|
|
|
0.15–0.57 |
p-Acetylacetophenone |
1009-61-6 |
|
|
|
|
|
|
|
|
|
|
0.19–0.29 |
2-Phenoxyethanol |
122-99-6 |
|
|
|
|
|
Coelution |
Acetone |
67-64-1 |
FFA 5 |
0.66–1.47 | 0.00−Coelution |
|
|
|
0.85–1.12 | 0.00–0.30 |
1.16–1.75 |
|
|
|
|
1.99–2.46 |
1.00–1.02 |
0.41–0.92 |
Propanol |
71-23-8 |
AA 1 FFA 9,10 |
|
|
|
0.60–1.30 |
|
|
|
0.48–0.53 |
Butanone |
78-93-3 |
FFA 1,2,6 |
0.00–0.41 |
0.00–0.38 |
|
0.00–0.50 |
|
0.00–0.97 |
| |
0.00–0.64 |
3.20–3.43 |
0.58–0.67 |
0.79–4.82 |
γ-Caprolactone |
695-06-7 |
N 2 |
10.11 |
AA |
1 |
|
|
|
|
|
|
|
|
0.00–2.11 |
Heptanone |
110-43-0 |
FFA 3,6 |
|
|
|
|
0.17 |
0.25–1.03 |
|
0.27–0.32 |
0.46–0.48 |
0.24–0.35 |
Isoamyl isovalerate |
659-70-1 |
|
|
|
|
|
|
|
|
|
0.00–0.51 |
2-Methyl-3-heptanone |
13019-20-0 |
|
|
|
|
|
6.85 |
0.00–6.50 |
|
|
|
|
Isobutyl-2-heptenone |
- |
|
|
|
|
|
|
0.00–0.17 |
0.00–0.09 |
(E)-β-Ionone |
79-77-6 |
CAR 3 |
|
|
|
|
|
|
0.11–0.12 |
|
Butyl hexanoate |
626-82-4 |
|
|
|
|
|
|
|
|
|
0.00–7.48 |
2-Propenyl hexanoate |
123-68-2 |
|
|
|
|
|
0.82 |
|
|
|
|
Hexyl hexanoate |
6378-65-0 |
|
|
|
|
|
|
|
|
|
0.00–3.33 |
Octyl hexanoate |
4887-30-3 |
|
|
|
|
|
|
0.00–1.75 |
|
|
|
Methyl salicylate |
119-36-8 |
|
|
|
|
|
|
|
|
0.04–0.05 |
0.00–0.50 |
5-Isobutylnonane |
|
|
0.29–0.29 |
|
2-Acetylfuran |
1192-62-7 |
|
|
|
|
|
Coelution |
0.00–Trace |
|
|
|
2-Propylfuran |
4229-91-8 |
|
0.53–0.71 |
0.49–0.61 |
0.75–0.85 |
|
|
|
|
|
|
2-Propionylfuran |
3194-15-8 |
|
0.44–0.66 |
0.00–0.78 |
0.53–0.69 |
|
|
|
|
|
|
2-Propanol |
67-63-0 |
|
|
|
|
2-Pentylfuran | |
3-Hydroxy-3-methyl-2-butanone | |
115-22-0 |
|
|
3777-69-3 | |
|
0.48–0.57 |
|
| 0.00–0.15 |
FFA | |
|
0.00−Coelution |
|
|
2,3,4,5 |
|
|
| |
|
|
0.00–0.91 |
0.60–0.78 |
1.72–1.91 |
0.61–1.43 |
1,2-Propanediol |
57-55-6 |
|
|
|
|
|
|
0.00–0.04 |
|
|
|
|
Pentanone |
107-87-9 |
FFA 1,6 |
|
|
|
0.00–1.20 |
|
|
|
|
|
Total |
|
|
1.37–1.64 |
1.23–2.02 |
0.00–Coelution1.43–1.97 |
0.00–5.70 |
|
0.00–0.91 |
0.60–0.78 |
2.02–2.21 |
0.61–1.43 | |
|
0.34–0.36 |
0.00–1.07 |
Methoxy-phenyl-oxime |
- |
0.43–0.88 |
0.00–0.62 |
0.00–0.72 |
|
|
|
|
3.39–3.60 |
2-Methylpropanol |
78-83-1 |
AA 9,11 |
|
|
|
0.00–0.50 |
|
3-Pentanone |
96-22-0 |
|
| |
|
|
|
β-Myrcene |
123-35-3 |
CAR |
γ-Methyl-γ-caprolactone2 |
2865-82-9 |
|
1.160.87 |
0.00–1.63 |
|
|
|
2,4-Dimethylbenzenamine | |
|
|
|
| |
|
|
|
|
95-68-1 |
0.00–0.26 |
|
|
|
|
|
|
0.00–0.60 |
0.00–0.25 |
0.00–0.35 |
|
|
|
|
|
|
1-Methoxy-2-Propanol |
107-98-2 |
|
|
|
|
|
2,3-Pentanedione | |
|
0.00–0.28 |
600-14-6 |
FFA | |
6 | |
|
Geranylacetone | |
|
|
689-67-8 |
|
0.00–0.69 |
|
0.00–0.30 |
0.42 |
0.00–1.05 |
|
|
|
|
0.96–1.21 |
|
|
0.00–0.48 |
0.46–0.83 |
|
|
|
|
|
|
|
|
|
|
4-Hydroxy-2-hexenoic acid lactone |
2407-43-4 |
|
|
0.00–0.17 |
|
|
|
o-Xylene |
95-47-6 |
FFA 1,2,4 |
0.95–1.16 |
1.14–1.73 |
Furfural1.13–1.45 |
98-01-1 |
|
|
|
Coelution |
|
|
|
|
Nonane |
111-84-2 | |
|
FFA | |
0.00–0.05 |
|
|
|
|
4 |
0.75–0.95 |
1.00–1.37 |
0.77–1.17 |
|
|
|
|
0.16–0.17 |
Elemol |
639-99-6 |
2-(Trimethylsilylethynyl)pyridine |
86521-05-3 |
|
|
|
|
|
|
0.00–0.40 |
|
|
0.34–0.36 |
|
2-Phenyl-2-propanol |
617-94-7 |
|
|
|
|
|
|
|
|
|
0.38–0.41 |
|
|
|
|
|
2.71 |
|
|
|
γ-Octalactone |
104-50-7 |
FFA 1 |
Trace |
0.00-Trace |
|
Total |
|
0.72–1.72 |
1.18–1.37 | |
|
0.72–1.80 |
1.26–3.40 |
0.42 |
0.00–1.50 |
0.00–1.92 |
3.39–3.60 |
0.00–0.16 |
m-Xylene |
108-38-3 |
FFA 1 |
|
|
|
|
1.25 |
|
|
|
|
Hexanal |
66-25-1 |
FFA 1,2,3,4,6,7,8,9,10 |
12.76–16.71 |
9.77–11.27 |
15.88–18.6 |
1-[1-Methyl-2-(2-propenyloxy)ethoxy]-2-propanol | 1.50–6.10 |
0.93 |
27.22–54.12 |
|
55956-25-7 | 10.28–13.85 |
40.78–40.88 |
1.29–25.07 |
3-Methylnonane |
5911-04-6 |
|
0.00–0.52 |
0.56–0.80 |
|
|
|
|
|
|
|
|
|
|
|
α-Muurolol |
|
|
0.00–0.09 |
19435-97-3 |
|
|
|
|
|
2.94 |
|
|
|
γ-Nonalactone |
104-61-0 |
FFA 1 |
1.31 |
0.00–0.33 |
| |
|
|
|
|
|
4-Ethyl-m-xylene |
874-41-9 |
|
|
|
|
|
|
|
0.05–0.07 |
|
0.00–0.64 |
2-Ethylhexanal |
123-05-7 |
|
|
|
|
|
4-Methylnonane | |
|
|
|
17301-94-9 | |
|
0.00–0.94 |
0.95–1.64 |
| 0.00–0.16 |
Butanol |
71-36-3 |
FFA |
t-Muurolol9,10 |
|
|
19912-62-0 |
|
|
|
|
|
|
4.32–4.72 |
|
|
|
|
|
|
|
|
7.45 |
|
4-Hydroxy-2-noneic acid lactone |
21963-26-8 |
FFA | |
1 | |
0.72 |
0.00–1.04 |
|
|
|
p-Cymene |
99-87-6 |
|
|
|
|
|
Trace |
|
0.32–0.33 |
|
(E)-2-Hexenal |
6728-26-3 |
FFA 1,2,4,8,9,10 |
0.00–1.60 |
0.00–1.67 |
0.00–1.75 |
|
|
0.00–0.19 |
|
|
|
|
3,7-Dimethylnonane |
17302-32-8 |
|
|
|
|
α-Cadinol |
481-34-5 |
|
|
|
|
|
Coelution |
|
δ-Undecalactone | |
710-04-3 |
N 2 | |
|
|
|
0.18–0.19 |
|
|
|
|
|
Styrene |
100-42-5 |
FFA 1,2,3; N 2,3 |
32.55–45.47 |
Heptanal |
111-71-7 |
FFA 2,3,7,8,9,10 |
0.00–0.7530.88–31.76 |
38.75–47.57 |
0.70–2.20 |
3,7-Dimethyl-decane |
17312-54-8 |
2-Butanol |
78-92-2 |
|
|
|
|
|
|
|
|
0.00–0.47 |
0.19–0.20 |
1.29–1.38 |
|
0.00–1.90 |
0.00–0.82 |
0.00–0.95 |
0.00–0.60 |
|
|
1.13–5.31 |
11.36–13.79 |
Decane |
124-18-5 | 0.00–1.90 |
|
1.04–1.14 |
1.10–1.14 |
0.00–1.91 |
FFA | 2,4 |
2.66–4.27 |
4.78–6.55 |
1.60–1.86 |
|
2-Methylbutanol |
Hexanone |
591-78-6 |
FFA 6 |
|
|
|
|
|
|
|
0.03–0.04 |
|
|
|
|
137-32-60.67–0.70 |
|
AA 5,8,9,110.95–3.88 |
|
|
|
|
β-Eudesmol |
473-15-4 |
|
0.06–0.34 |
|
|
|
|
|
Trace |
|
|
|
Total |
|
|
14.76 | 3.52–4.80 |
|
0.38–5.48 |
0.00–3.18 |
2.30–3.52 |
1.21–1.50 |
0.22–2.47 |
α-Methylstyrene |
98-83-9 |
|
0.00–0.43 |
3-Methylbutanol |
β-Linalool |
78-70-6 |
| 0.00–0.38 |
0.00–0.49 |
(E)-2-Heptenal |
18829-55-5 |
FFA 1,2,4,8,9,10 |
1.52–1.75 |
1.54–2.01 |
|
|
|
1.52–1.88 |
123-51-3 |
AA 5,7,8,9,11 |
0.00–0.80 |
0.58–0.86 |
|
|
4-Methyldecane | 0.00–2.60 |
|
0.00–0.58 |
|
|
1.79–1.97 |
|
2847-72-5 |
|
0.00–0.75 |
0.42 |
0.06–0.22 |
|
1.97–2.43 |
|
0.12–3.23 |
Total |
|
|
38.51–49.28 |
38.24–38.51 |
43.41–50.72 |
3.50–6.70 |
1.25 |
0.00–0.60 |
1.07–1.27 |
14.15–16.89 |
0.68–7.75 |
1 [26];
2 [25];
3 [31];
4 [33][34]. FFA, free fatty acids; N, naturally present (not considered as a contaminant). The value “min–max” corresponds to the minimum and maximum percentages for each volatile compound identified. “Black bean” refers to the 3 cultivars studied, and “Pinto bean” and “Dark red kidney bean” correspond to 2 cultivars for each
[25]. For peas, “Whole” corresponds to 3 different harvest years of the cultivar Eclipse (2005, 2006, and 2007)
[
0.64–1.34 |
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
0.11–0.79 |
(E,E)-2,4-Heptadienal |
4313-03-5 |
FFA 2,8,9,10 |
0.57–0.66 |
0.57–0.59 |
0.00–0.71 |
|
Menthol |
1490-04-6 | |
Trace |
0.00−Coelution |
|
|
|
|
2,4-Dimethyldecane |
2801-84-5 |
|
|
|
|
|
|
|
|
|
|
|
|
0.28–0.45 |
0.00–0.60 |
|
Octanal |
124-13-0 |
FFA 2,7,8,9,10 |
0.00–0.62 |
|
0.00–0.68 |
|
|
0.00–0.58 |
1.35–1.76 |
2.07–2.40 |
1.15–1.29 |
0.08–2.22 |
|
|
0.00–0.32 |
Octanone |
|
|
|
|
|
|
0.00–0.31 |
|
|
|
111-13-7 |
FFA 6 |
|
|
|
|
0.41 |
|
|
|
|
p-Menth-1,5-dien-8-ol | |
1686-20-0 |
|
|
|
|
|
Coelution |
(E)-2-Octenal |
2548-87-0 |
FFA 1,3,7,8,9,10 |
|
|
|
Undecane |
1120-21-4 |
FFA 1,4 | 3.00–13.10 |
0.00–0.87 |
1.06–1.51 |
|
1.80–2.60 |
0.00–0.10 |
2.13–2.16 |
|
0.23–0.23 |
0.48–0.51 |
0.19–0.45 |
|
0.15–0.15 |
1.36–1.52 |
|
Dodecane |
112-40-3 |
|
0.00–1.12 |
1.22–1.27 |
|
0.80–3.60 |
|
|
|
0.57–0.62 |
3-Phenyl-2-butanol |
52089-32-4 |
|
|
|
|
|
|
|
0.00–1.23 |
|
|
|
2,3-Butanediol |
513-85-9 |
|
|
|
|
|
|
|
|
0.39–0.40 |
|
0.00–1.72 |
Pentanol |
71-41-0 |
FFA 2,3,4,7,8,9,10 |
0.00–1.61 |
0.00–0.62 |
|
|
1.52 |
1.17–3.89 |
4.90–4.98 | 1.85–2.29 |
0.74–1.57 |
|
|
|
3-Octanone |
106-68-3 |
FFA 4,6 |
|
| 1.28–1.36 |
|
|
Trace |
|
|
|
|
|
Nonanal |
124-19-6 |
FFA 2,4,6,7,8,9,10 |
2.11–3.08 |
2.42–2.80 |
2.13–3.60 |
|
2-Pentanol |
6032-29-7 |
FFA 1.30 |
3.12–5.24 |
3.70–4.60 |
9.8–12.31 |
7.99–10.54 |
3.54–36.29 |
|
9 |
| 0.80–3.22 |
|
|
|
0.23 |
|
|
3-Octen-2-one |
1669-44-9 |
FFA | 0.18–0.27 |
|
0.00–0.46 |
5 |
|
|
|
|
|
0.28–0.83 |
|
|
0.69–0.86 |
|
(E)-2-Nonenal |
18829-56-6 |
FFA 2,7,9,10 |
0.00–0.67 |
0.00–0.58 |
|
2,4-Dimethyldodecane |
6117–99–3 |
FFA |
|
|
|
0.20–0.26 |
|
1 |
0.14–2.52 |
3-Methyl-3-pentanol | |
77-74-7 |
|
|
|
|
|
|
|
2,3-Octanedione |
585-25-1 |
62185-53-9 |
|
|
|
|
|
|
|
0.00–3.10 |
|
|
|
Total |
|
|
2.06–4.77 |
3.91–6.89 |
1.06–1.07 |
0.30–0.70 |
13.77 |
0.00–0.11 |
1.35–1.63 |
0.11–12.73 |
0.09–0.09 |
|
0.00–0.33 |
|
5.34 |
0.00–0.60 |
|
|
|
|
|
|
|
|
|
Trace |
0.00–1.34 |
1.71–2.00 |
|
0.52–0.53 |
|
4-Oxononanal |
74327-29-0 |
|
|
|
|
|
|
|
0.72–0.91 |
|
|
|
5,8-Diethyldodecane |
24251-86-3 |
|
(E,E)-3,5-Octadien-2-one |
30086-02-3 | |
|
|
1-Penten-3-ol | |
|
|
|
616-25-1 | 0.04–0.06 |
|
|
FFA | 2,3,4,8,9,10 |
0.99–1.86 |
1.34–1.88 |
2.30–2.64 |
|
6.87 |
0.44–5.58 |
|
|
|
|
FFA 2,5 |
1.14–1.98 |
4-Dodecanoyloxybutyl dodecanoate |
624-07-7 |
|
1.31–2.41 |
1.42–1.46 |
|
|
|
0.00–8.00 |
|
|
|
0.20–0.28 |
|
0.16–0.20 |
0.00–0.77 |
|
|
(E,E)-2,4-Nonadienal |
5910-87-2 |
FFA 7,9,10 |
|
|
|
|
|
|
0.00–0.44 |
|
|
|
2,6,10-Trimethyldodecane |
3891-98-3 |
|
0.00–0.79 |
0.64–1.27 |
|
|
|
|
|
|
|
|
2-Penten-1-ol |
20273-24-9 |
|
|
|
|
|
|
0.00–3.84 |
|
|
|
Nonanone |
821-55-6 |
|
|
|
|
|
Isopropyl myristate |
110-27-0 |
|
| |
|
|
|
| 0.26 |
|
|
|
|
|
0.44–0.53 |
|
|
Decanal |
112-31-2 |
FFA 2,7,10 |
0.81–1.59 |
0.00–1.06 |
Tridecane0.72–0.99 |
629-50-5 |
|
|
|
Coelution |
Coelution−1.33 |
1.28–1.33 |
2.86–3.26 |
0.90–4.30 |
|
|
1.15–1.41 |
0.06–0.08 |
|
5-[3-(4-Methoxyphenyl)-2-oxaziridinyl]-1-pentanol | 0.37–6.16 |
0.00–0.15 |
- |
|
|
|
|
|
|
|
0.33–0.90 |
|
Decanone |
693-54-9 |
3-Hydroxy-ethyl mandelate |
- | |
|
|
|
0.28–0.42 |
|
|
0.00–0.35 |
0.34–0.45 |
|
|
|
(Z)-2-Decenal |
2497-25-8 |
FFA |
0.00–0.42 |
|
|
|
|
|
|
7,10 |
|
|
|
|
|
2-Methyltridecane |
1,6-Dioxacyclododecane-7,12-dione1560-96-9 |
FFA |
0.79–1.15 |
|
|
|
1 |
|
|
|
|
|
|
|
0.05–0.05 |
|
0.00–0.14 |
777-95-7 |
|
|
|
|
Total | |
|
|
0.42–0.66 |
0.45–0.66 | |
|
0.00–0.77 |
0.00–1.20 |
1.750.00–0.72 |
|
|
|
1.75–17.25 |
1.50–5.59 |
0.04–0.05 |
(E,E)-2,4-Decadienal |
25152-84-5 |
FFA 3,7,9,10 |
|
|
|
0.00–24.15 |
3-Methyltridecane | |
Trace |
|
|
6418-41-3 | |
|
|
FFA | 1 |
|
|
|
|
|
|
|
0.12–0.15 |
|
0.00–0.42 |
Undecanone |
112-12-9 |
|
|
|
|
|
Trace |
0.00–0.18 |
|
|
|
Undecanal |
112-44-7 |
|
|
|
|
|
|
|
|
0.22–0.26 |
|
0.00–1.61 |
|
2,2-Dimethyltridecane |
61869-04-3 |
|
|
|
|
|
|
|
|
0.13–0.15 |
|
|
2-Butyl-1,3,2-dioxaborinan-4-one |
33823-94-8 |
|
|
|
|
|
|
|
0.00–0.37 |
|
|
Tetradecane |
629-59-4 |
|
|
|
|
0.00–1.10 |
Trace |
0.00–1.10 |
|
1.30–1.90 |
|
0.48–1.34 |
Pentadecane |
629-62-9 |
|
|
|
|
|
|
0.00–1.57 |
|
0.19–0.21 |
|
0.00–0.64 |
|
|
Phenol |
108–95–2 |
|
0.00–0.47 |
0.31–0.34 |
|
| |
3-Methylpentadecane |
2882-96-4 |
|
|
|
|
|
|
|
|
0.15–0.26 |
|
0.00–0.08 |
Hexadecane |
544-76-3 |
|
|
|
|
|
|
0.00–2.75 |
|
0.24–0.26 |
|
0.00–0.35 |
Heptadecane |
629-78-7 |
|
|
|
|
|
1.27 |
|
|
0.07–0.10 |
|
|
Nonadecane |
629-92-5 |
|
|
|
|
|
|
|
|
0.02–0.06 |
|
0.46–0.99 |
Tetracosane |
646-31-1 |
|
|
|
|
|
|
|
0.00–0.57 |
|
|
|
|
0.00−Coelution |
0.54–0.70 |
|
|
|
Benzyl alcohol |
100-51-6 |
AA 5,11 |
0.00–0.24 |
0.26–1.11 |
|
|
|
0.00−Coelution |
|
0.54–0.54 |
|
0.58–1.46 |
Hexanol |
111-27-3 |
FFA 2,3,4,6,7,8,9,10 |
1.58–1.86 |
1.39–1.60 |
1.24–1.25 |
|
4.54 |
0.88–9.53 |
|
10.64–11.32 |
3.87–4.29 |
0.33–31.41 |
Dodecanal |
112-54-9 |
|
|
|
|
|
|
|
|
|
|
0.00–0.89 |
2-Ethylhexanol |
104-76-7 |
|
0.29–0.45 |
0.29–0.66 |
0.00–0.4 |
|
|
0.00–1.39 |
|
|
|
0.00–9.38 |
Total |
|
|
4.95–6.90 |
4.74–5.38 |
4.73–5.62 |
0.50–1.20 |
12.01 |
1.69–21.96 |
3.24–3.25 |
7.59–8.42 |
4.48–4.53 |
3.72–7.46 |
Tetradecanal |
124-25-4 |
|
|
|
|
|
0.63 |
|
0.26–0.55 |
4-Ethylcyclohexanol |
4534-74-1 |
|
|
|
|
|
|
|
|
0.15–0.17 |
|
|
2,3-Dimethylcyclohexanol |
1502-24-5 |
|
|
|
|
|
|
|
|
|
|
0.00–0.20 |
1-Hexen-3-ol |
4798-44-1 |
|
|
|
|
|
0.29 |
0.00–0.14 |
|
|
|
|
(Z)-3-Hexen-1-ol |
928-96-1 |
FFA 8,9 |
|
|
|
|
4.23 |
0.00–0.29 |
|
|
|
|
(Z)-4-Hexen-1-ol |
928-91-6 |
|
|
|
|
|
|
0.00–0.33 |
|
|
|
|
Total alkanes |
|
|
7.84–15.66 |
16.43–20.00 |
7.95–8.09 |
7.30–14.30 |
1.27 |
0.00–5.44 |
0.31–0.57 |
4.37–5.22 |
4.06–4.41 |
4.61–9.22 |
(E)-5-(Pentyloxy)-2-pentene |
34061-80-8 |
|
|
|
|
|
|
0.00–0.69 |
|
|
|
|
(Z)-1-Methoxy-3-hexene |
70220-06-3 |
|
|
|
|
|
|
|
0.00–1.91 |
|
|
Heptanol |
Cyclohexanone | |
|
0.00–0.39 |
111-70-6 |
FFA | 8,9,10 |
|
|
|
0.00–1.20 |
Coelution |
Coelution−0.66 |
|
0.32–0.36 |
0.50–0.54 |
0.00–0.26 |
2-Heptanol |
543-49-7 |
FFA 9 |
|
|
|
0.00–0.40 |
|
|
|
|
|
|
2-Methyl-3-heptanol |
18720-62-2 |
|
|
|
|
|
0.72 |
|
|
|
|
|
1 [26];
2 [31];
3 [32];
4 [35];
5 [12];
6 [33][34]. AA, amino acids; FFA, free fatty acids; CAR, carotenoids. The value “min–max” corresponds to the minimum and maximum percentages for each volatile compound identified. “Black bean” refers to the 3 cultivars studied, and “Pinto bean” and “Dark red kidney bean” correspond to 2 cultivars for each
[25]. For peas, “Whole” corresponds to 3 different harvest years of the cultivar Eclipse (2005, 2006, and 2007)
[26], “Dehulled” corresponds to dehulled pea flour
[27], and “Protein” refers to protein concentrate (dry process)
[28] and protein isolate (wet process)
[27]. “Chickpea” refers to 2 cultivars
[29]. For faba beans, “Tannin” corresponds to a group of low-tannin cultivars and a group of high-tannin cultivars
[30], “Location” corresponds to different low-tannin cultivars that were harvested at 2 different locations in Canada
[31], and “Storage” corresponds to high-tannin cultivars that were stored under 3 different conditions (ambient, positive, and negative temperatures) for 60 days and a control (sample stored for 0 days)
[32] (see
Table 1 for more details).
Table 7. Acids in pulses (expressed as percentages).
Acids |
CAS |
Origin (s) |
Pea |
Chickpea |
Faba Bean |
Dehulled |
Proteins |
Tannin |
Storage |
Acetic acid |
64-19-7 |
AA 2,3,4 |
|
|
3.10–3.90 |
1.84–2.35 |
0.49–1.94 |
2-Methylbutanoic acid |
116-53-0 |
N 1; AA 1,2,4 |
|
0.00–0.22 |
|
0.13 |
0.00–0.26 |
3-Methylbutanoic acid |
503-74-2 |
|
3-Methyl-2-heptanol |
31367-46-1 |
|
|
|
|
0.00–2.40 |
|
|
|
|
|
|
3-Ethyl-2-methyl-1,3-hexadiene |
61142-36-7 |
|
|
|
|
|
|
0.00–0.05 |
|
|
0.37–0.42 |
|
2-Hepten-4-ol |
4798-59-8 |
|
|
|
|
|
|
|
0.00–0.78 |
|
|
|
1-Tetradecene |
1120-36-1 |
|
|
|
|
|
5.74 |
0.00−Coelution |
|
0.07–0.08 |
|
Octanol |
111-87-5 |
FFA 3,7,8,9,10 |
0.00–0.33 |
0.29–0.61 |
0.00–0.29 |
3.7–10.7 |
1.16 | |
0.82–1.29 |
|
0.24–0.28 |
1.18–1.48 |
0.35–0.83 |
Total alkenes |
|
|
|
|
|
|
5.74 |
0.05–0.69 |
3-Octanol |
589-98-0 |
FFA1 |
|
|
|
0.00–1.3 |
|
|
|
|
|
0.00–0.42 |
1-Octen-3-ol |
3391-86-4 |
FFA 2,3,4,6,7,8,9,10 |
1.18–1.43 |
1.23–1.60 |
0.00–3.51 |
|
2.61 |
1.23–1.38 |
|
0.35–0.41 |
3.93–4.00 |
0.29–1.64 |
(E)-2-Octen-1-ol |
18409-17-1 |
FFA 10 |
|
1 [32];
2 [35];
3 [34]. FFA, free fatty acids; AA, amino acids. The value “min–max” corresponds to the minimum and maximum percentages for each volatile compound identified. “Black bean” refers to the 3 cultivars studied, and “Pinto bean” and “Dark red kidney bean” correspond to 2 cultivars for each
[25]. For peas, “Whole” corresponds to 3 different harvest years of the cultivar Eclipse (2005, 2006, and 2007)
[26], “Dehulled” corresponds dehulled pea flour
[27]
1 [26];
2 [35];
3
1 [31];
2 [28];
3 [32];
4 [35];
5 [33]. FFA, free fatty acids. The value “min–max” corresponds to the minimum and maximum percentages for each volatile compound identified. “Black bean” refers to the 3 cultivars studied, and “Pinto bean” and “Dark red kidney bean” correspond to 2 cultivars for each
[25]. For peas, “Whole” corresponds to 3 different harvest years of the cultivar Eclipse (2005, 2006, and 2007)
[26], “Dehulled” corresponds to dehulled pea flour
[27], and “Protein” refers to protein concentrate (dry process)
[28] and protein isolate (wet process)
[27]. For faba beans, “Tannin” corresponds to a group of low-tannin cultivars and a group of high-tannin cultivars
[30], “Location” corresponds to different low-tannin cultivars that were harvested at 2 different locations in Canada
[
1 [27];
2 [30]. FFA, free fatty acids; N, naturally present (not considered as a contaminant). The value “min–max” corresponds to the minimum and maximum percentages for each volatile compound identified. For peas, “Dehulled” corresponds to dehulled pea flour
[27], and “Protein” refers to protein concentrate (dry process)
[
The value “min–max” corresponds to the minimum and maximum percentages for each volatile compound identified. “Black bean” refers to the 3 cultivars studied, and “Pinto bean” and “Dark red kidney bean” correspond 2 cultivars for each
[25]. For peas, “Whole” corresponds to 3 different harvest years of the cultivar Eclipse (2005, 2006, and 2007)
[26], “Dehulled” corresponds to dehulled pea flour
[27], and “Protein” refers to protein concentrate (dry process)
[28] and protein isolate (wet process)
[27]. “Chickpea” refers to 2 cultivars
[29]. For faba beans, “Tannin” corresponds to a group of low-tannin cultivars and a group of high-tannin cultivars
[30], and “Storage” corresponds to high-tannin cultivars that were stored under 3 different conditions (ambient, positive, and negative temperatures) during 60 days and a control (sample stored for 0 days)
[32]. No other volatile was detected in “location” faba beans (see
Table 1 for more details).
5. Odour-Active Compounds in Pulses
An odour-active compound is a volatile compound whose concentration is greater than or equal to its odour detection threshold. It contributes to the product’s aroma. These compounds can be detected by GC-O.
In dehulled peas, 15 odour-active compounds are present compared to 16 in pea protein isolates, and they are related to different types of odour descriptors, such as mushroom/earth, vegetable/green/pea, empyreumatic (peanut-grilled), animal, floral/fruity, and sweet
[27]. For lupin, 19 odour-active compounds (including an unknown volatile) were identified in whole grains and 26 in dehulled grains. These volatiles are described as sweet, beany/pea/green/cardboard, floral, mushroom, fruity/floral, and animal
[38][39]. Odour-active compounds are distributed into aldehydes, alcohols, ketones, acids, lactones, and pyrazines; however, aromatic hydrocarbons, alkanes, alkenes, esters, terpenes, and furans are not involved in the aroma of these pulses. The origin of these compounds is free fatty acid oxidation, except for acids and pyrazines, which are derived primarily from amino acid degradation.
Dehulled peas and pea isolates share the following odourant compounds: vanillin, hexanal, (E,E)-2,4-decadienal, 1-octen-3-ol, 2,3-octanedione, undecanone, γ-octalactone, 4-hydroxy-2-noneic acid lactone, 5- or 6-methyl, and benzothiazole. Some compounds are not detected in whole peas but are active compounds in pea protein isolates, such as 4-ethybenzaldehyde, phenylacetaldehyde, 3-methylthiopropanal, heptanal, (E)-2-octenal, (E,E)-3,5-octadien-2-one, heptanoic acid, and dimethyl trisulfide; they mainly come from free fatty acids and amino acids. However, nonanal, pentanol, octanol, nonanol, 3-methylbutanoic acid, and γ-nonalactone are only active in dehulled peas; they mainly come from free fatty acid oxidation. Curiously, nonanal, pentanol, and octanal are more concentrated in volatile extracts of pea protein isolates than dehulled peas but are only perceived as odour-active in dehulled samples.
Whole and dehulled lupins have only a few odour-active compounds in common: (E)-2-nonenal, (E,Z)-2,6-nonadienal, 1-octen-3-one, 3-isobutyl-2-methoxypyrazine, and 3-isopropyl-2-methoxypyrazine. Many compounds from amino acids are only present in dehulled lupin, such as 2-acetyl-1-pyrroline, maltol, sotolone, and some acids. They are probably due to contamination by microorganisms in these grains.
Vanillin and gama-octalactone are odour-active compounds in peas and dehulled lupins. Gama-octalactone is described as floral/anise/mint in peas and coconut/sweet in lupins. Hexanal is not an odourant only in dehulled peas. Pea protein isolates and whole lupins have two odourant compounds in common: (E)-2-octenal and dimethyl trisulfide; this last compound is described as faeces/meat broth/sewer in peas and meaty/metallic/sulphur in lupins. 3-Methylbutanoic acid and -nonalactone are odour-active compounds of whole peas and dehulled lupins; 3-methylbutanoic acid is perceived as animal in peas but sweaty/fruity/cheesy in lupins. These differences are not necessarily due to the variety of pulses; the descriptors depend on the panellists, the possible presence of coelution, or large differences in the volatile concentrations.
Odour-active compounds present in peas and lupins are derived mainly from free fatty acids and amino acids. The large variety of these perceived volatiles depends on the type of pulses, the cultivar, the storage conditions, and the transformation steps. Finally, descriptors for the same molecule could be very different and depend on the studied matrix.
6. Conclusions and Perspectives
A qualitative comparison of volatile compounds between pulses is presented. Indeed, the main drawback to making quantitative comparisons of volatiles is that the data are often expressed as peak areas or relative percentages, without using a standard compound allowing real quantification of each volatile compound. However, it was possible to suggest some hypotheses on the origins of the off-notes present in pulses with the aim of increasing the acceptability of pulses in food for humans.
The diversity of unsaturated free fatty acid contents and the characteristics of endogenous lipoxygenases in pulses mainly explain the large variety of volatile compounds identified. All of the classes of volatiles are present in pulses, but ketones, pyrazines, furans, and lactones are minority classes. Aromatic hydrocarbons represent more than 38% of the volatiles detected in common beans (black beans, pinto beans, and dark red kidney beans), whereas aldehydes and alcohols are more specific to dehulled peas, pea proteins (concentrate and isolate), and faba beans (location and storage). Seed transformations or uncontrolled parameters of storage promote the generation of volatile compounds from the degradation of free fatty acids and amino acids. For whole peas, the 2006 harvest-year seeds present higher percentages of aromatic hydrocarbons, aldehydes, alkanes, ketones, and furans than those of the 2005 and 2007 seeds
[13]. If the storage conditions are supposed to be equivalent for these three harvest years, bad culture conditions could be suggested during 2006, such as water stress and/or mechanical or insect attacks, compared to years 2005 and 2007 and could explain these differences in terms of volatiles. Finally, all of these parameters could account for such heterogeneity in volatile compounds, yet they are not
always taken into consideration in explaining the variability in aromatic composition.
Although the number of volatile compounds identified in pulses is high, only a small part contributes to the aroma. These odour-active compounds present different descriptors and threshold detection. However, identifying odour-active compounds in pulses is rarely done, and only two studies report on their olfactory impact, namely in lupins and peas. Only aldehydes, alcohols, ketones, acids, lactones, and pyrazines are involved in the aroma. The origin of these compounds is free fatty acid oxidation, except for acids and pyrazines, which originate primarily from amino acid degradation by unwanted microorganisms. Off-notes are described as vegetable, green, hay, potato, bean, metallic, mushroom, animal, dust, solvent, cardboard, etc., and refer to “beany” notes, but other volatiles present a pleasant smell, such as floral, fruity, grilled, sweet, and vanilla odours.
Precise identification of the odour-active compounds in pulses could allow the determination of their main origins and the proposal of strategies to reduce their perception. Some strategic axes have been identified to improve pulses’ aroma: to limit the production of volatile compounds, to remove the off-notes, and to decrease the perception of off-notes
[40][41]. One approach consists of generating lipoxygenase-free legume seeds to limit off-note production, and this experiment was carried out on soybeans
[42]. However, volatiles provided by the LOX pathway are also fully involved in a mechanism of defence for plants
[43]. Therefore, a potential lower resistance of mutated plants should be considered. Moreover, due to climate change, water stress, or other stressors increase in future years, these new cultivars could be less adapted and produce lower yields. Moreover, heat treatments, such as blanching, microwave, radiofrequency, and conventional heating of mature seeds, allow the decrease or inhibition of lipoxygenase activity
[44][45]. However, high temperatures favour the autoxidation of unsaturated free fatty acids. A compromise must be considered to limit these two phenomena. Finally, for the past 20 years, fermentation has modified the aroma profile of pulses by reducing or masking off-notes. Some molecules are still detected, such as pentanal, hexanal and heptanal in fermented lupin proteins or 2,3-butanedione, hexanal, 1-penten-3-one,2-heptanone, and 3-methylbutanol in fermented pea proteins
[46][47]. A perspective that must be studied is the use of microorganism coculture to improve the aroma of pulses
[48]. Another approach could consist of using perceptual interactions to mask off-notes or modify the aroma product to a pleasant product, in particular using odour-mixture, odour-taste, and/or odour-texture interactions
[49][50].
Furthermore, non-volatile compounds also contribute to the off-flavours of pulses, particularly for bitterness and astringency (off-tastes). Saponins, alkaloids, and phenolic compounds have been identified in pulses, but their role in sensorial perception has rarely been studied. The elimination of these molecules could increase the acceptability of plantbased products.