Research ArticleDetermination of Volatile Compounds in Four CommercialSamples of Japanese Green Algae Using Solid PhaseMicroextraction Gas Chromatography Mass Spectrometry
Masayoshi Yamamoto1 Susanne Baldermann23 Keisuke Yoshikawa4 Akira Fujita4
Nobuyuki Mase5 and Naoharu Watanabe1
1 Integrated Bioscience Section Graduate School of Science and Technology Shizuoka University 836 Ohya Suruga-kuShizuoka 422-8529 Japan
2 Leibniz-Institute of Vegetable and Ornamental Crops GroszligbeerenErfurt eV Theodor-Echternmeyer-Weg 114979 Groszligbeeren Germany
3 Institute of Nutritional Science University of Potsdam Arthur-Scheunert-Allee 114-116 14558 Nuthetal Germany4Technical Research Institute RampD Center T Hasegawa Company Ltd 29-7 Kariyado Nakahara-ku Kawasaki 211-0022 Japan5 Graduate School of Engineering Shizuoka University 3-5-1 Johoku Naka-ku Hamamatsu 432-8561 Japan
Correspondence should be addressed to Naoharu Watanabe acnwataipcshizuokaacjp
Received 31 August 2013 Accepted 6 October 2013 Published 27 January 2014
Academic Editors M A Strege T Tuzimski and M C Yebra-Biurrun
Copyright copy 2014 Masayoshi Yamamoto et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited
Green algae are of great economic importance Seaweed is consumed fresh or as seasoning in Japan The commercial value isdetermined by quality color and flavor and is also strongly influenced by the production area Our research based on solid phasemicroextraction gas chromatography mass spectrometry (SPME-GC-MS) has revealed that volatile compounds differ intenselyin the four varieties of commercial green algae Accordingly 41 major volatile compounds were identified Heptadecene wasthe most abundant compound from Okayama (Ulva prolifera) Tokushima (Ulva prolifera) and Ehime prefecture (Ulva linza)Apocarotenoids such as ionones and their derivatives were prominent volatiles in algae from Okayama (Ulva prolifera) andTokushima prefecture (Ulva prolifera) Volatile short chained apocarotenoids are among the most potent flavor components andcontribute to the flavor of fresh processed algae and algae-based products Benzaldehyde was predominant in seaweed fromShizuoka prefecture (Monostroma nitidum) Multivariant statistical analysis (PCA) enabled simple discrimination of the samplesbased on their volatile profiles This work shows the potential of SPME-GC-MS coupled with multivariant analysis to discriminatebetween samples of different geographical and botanical origins and form the basis for development of authentication methods ofgreen algae products including seasonings
1 Introduction
Seaweeds have been traditionally used as medicines foodand seasoning [1 2] Most seaweeds are of commercialimportance in foodstuffs cosmetics and dyes Moreoverthey serve as source for biological active compounds Today75ndash8 million tons of macroalgae are produced per annumand their estimated value is US$ 55ndash6 billion [3] Seaweedsare widely distributed throughout the world and are predom-inantly consumed in Japan China Korea South AustraliaNew Zealand Polynesia and South America [4]
Certain countries or regions have reputations for pro-ducing high-quality green algae including Aonori (a highquality merchandised Japanese green seaweed) and are ableto demand a significantly higher price for their productsIn Japan high-value production areas include the river Shi-manto in Kochi prefecture and river Yoshino in Tokushimaprefecture There is a strong interest in the authenticity ofthese commercial products and up to now consumers haveto rely on package information to provide confirmation thatthe product is from a high-quality region with a traceability
Hindawi Publishing Corporatione Scientific World JournalVolume 2014 Article ID 289780 8 pageshttpdxdoiorg1011552014289780
2 The Scientific World Journal
system such as the Food Marketing Research and Informa-tion Center in Japan [5]
GC-MS techniques coupled with multi-variant analysisare becoming increasingly important tools to monitor thedistribution of counterfeit foodstuffs and have been used inauthenticating many food products such as tea olive oilhoney cheese and wine [6ndash12]
We newly report on nontargeted SPME-GC-MS fol-lowed by multi-variant statistical analysis in Japanese greenmacroalgae Significant differences in the volatile profilesof green algae from four production areas were detectedimplying that markers could potentially be identified usingthis analytical-statistical approach
2 Experimental
21 Commercial Dried Green Algae Samples Ulva proliferaUlva linza and Monostroma nitidum commercially all soldas ldquoAonorirdquo (Japanese green algae) were subjected to sensoryevaluation and used for solid-phase microextraction (SPME)method development Ulva prolifera (2 samples) Ulva linzaand Monostroma nitidum were obtained from OkayamaTokushima Ehime and Shizuoka prefecture respectivelyCommercial Japanese green algae were purchased from awholesale agency in Japan The samples were placed in airtight plastic bags in the dark at room temperature Prior toanalysis the samples were ground to a fine powder usingliquid nitrogen
22 Sensory Evaluation The sensory tests were carried outby nine untrained panelists consuming regularly green algaeHedonic sensory attributes evaluated in this study were colortaste and overall acceptability of four green algae samplesThepanelists (6male 3 female) were between 26- and 40-yearold A nine point hedonic scale (0ndash8) anchored by dislikeextremely to like extremely for the overall score light coloredto strongly colored for the green color and weak to intensefor the taste was employedMore precisely the panelists wereasked to evaluate the following aroma attributes animalicfloral spicy fatty green note marine-like fresh (waterly)powdery and leather-like common flavor attributes of greenalgae Samples were served in glass beakers and providedrandomly to panelists Sensory evaluation procedures wereexplained to the panelists prior the tests
23 Solid Phase Microextraction (SPME) Polydimethylsilox-ane fibers (100 120583m) were mounted in a SPME manual holder(Supelco Bellefonte PA USA) All fibers were conditionedprior to analyses according to the manufacturerrsquos recom-mendations Various parameters (extraction method timeand temperature) influencing SPME analysis were optimizedFor each analysis 10 g of sample was placed in a 40 cm3 vialspiked with 1mg of the internal standard ethyldecanoateand then sealed with an aluminum crimp cap provided witha needle-pierceable polytetrafluoroethylenesilicone septumEach sample vial was placed at 50∘C for 60min to equilibrateand then the septum was pierced with the SPME needleFibers were exposed to the sample headspace for 60min
After the extraction time fibers were retracted into theneedle transferred immediately to the injection port of a GCand desorbed at 230∘C for 1min
24 GCMS Analysis The compounds collected in theheadspace above the green algae samples were analyzed byGC connected to a mass spectrometer (MS) (Shimadzu GC-MSQP5000) which was controlled by a Class-5000 worksta-tion Separation was carried out on a Supelcowax 10 fusedsilica capillary column 30m times 025mm id 025120583m filmthickness (Supelco Bellefonte PA USA) Injection was insplitless mode for 1min at 230∘C with a specific SPME insertTheGC temperaturewas raised from50 to 160∘Cat 3∘Cminminus1and from 160 to 240∘C at 10∘Cminminus1 The mass spectra werescanned at 70 eV over a mass range from mz 50 to 280Nonisothermal linear RI (Kovats type) was calculated afterthe analysis of a C11ndashC30 n-alkane series (GL Science) underthe same conditions Volatile compounds were tentativelyidentified by comparing their mass spectra with those of thereference database (NIST Mass Spectral Data 981015840 edition)Compounds were attributed to molecules through their indi-vidual mass spectrum retention indices (RI) and retentiontime (RT) In addition pure reference compounds were usedto confirm the results Flavor properties were assigned basedon reported odor descriptions [3 13 14]
25 Data Analysis The relative peak areas were calculatedin relation to the peak area of the internal standard ethylde-canoate The identified volatile compounds were classifiedinto different groups of molecules such as alkanes alkenesketones aldehydes sulfur compounds alcohols and estersUnidentified compounds were excluded from this analysisThe relative peak areas of the different compounds in eachcategory were calculated as a ratio of the total peak areaStatistical analyses were conducted using XL-STAT version2013 (Addinsoft New York USA)
3 Results and Discussion
The results of the sensory analysis revealed that it wasimpossible to differentiate between the samples based on theoverall score (Figure 1) The same applies also to taste andcolor (data not shown) Based on the nine aroma attributes(animalic floral spicy fatty green note marine-like fresh(waterly) powdery and leather-like) it was found that thesamples from Okayama Tokushima and Ehime prefectureare uniform However the sample from Shizuoka prefecturewas differently evaluated in respect of its green-note marine-like fresh and powdery aroma (Figure 2)
As a result it is impossible to distinguish between com-mercially sold ldquoAonorirdquo samples based on sensory evalua-tion Solely in taxonomically different samples OkayamaTokushima and Ehime (Ulva species) versus Shizuoka(Monostroma species) somewhat different scores could beobtained
Volatile compounds are fundamental for algae odor andaromaTherefore it is not surprising that volatile compoundsin algae have been investigated and reports evaluating volatile
The Scientific World Journal 3
Okayama EhimeTokushima0
2
4
6
8
Scor
e
Shizuoka
Figure 1 Overall scores of the sensory evaluation of green algaesamples
001020304050607080Animalic
Floral
Spicy
Fatty
Green noteMarine-like
Fresh
Powderly
Leather-like
OkayamaTokushima
EhimeShizuoka
Figure 2 Sensory characterisation of green algae samples Thefollowing aroma attributes were determined based on panelistrsquosevaluation animalic floral spicy fatty green note marine-likefresh (waterly) powdery and leather-like
metabolites for example in brown and red algae are availablein the current literature [15ndash18]
GC-MS techniques coupled with multi-variant analysishave been used in authenticating many food products andshould be tested in this study for its practicability to dis-tinguish different commercially sold Japanese green algaesamples
Forty-one major volatile compounds classed as alkanesalkenes ketones aldehydes sulfur compounds alcoholsand esters were identified in the four commercial Japanesegreen algae (Table 1) These compounds are derived from
00
200
400
600
800
1000Alkanes
Alkenes
Ketones
AldehydesSulfur compounds
Alcohols
Esters
OkayamaTokushima
EhimeShizuoka
Figure 3 Chemical classification of volatile compounds in relativeconcentrations (119899 = 3) in different commercial green algae samples
different precursors including the amino acids fatty acidsand carotenoids (Table 1)
Hydrocarbons including alkanes and alkenes (eg tetra-decene pentadecane hexadecane and octadecene) wereabundant in three (Okayama Tokushima and Ehime) of thefour samples (Figure 3)
The relative concentrations of alkenes vary among thesamples from different algae of the orderUlvales Green algaeof the Ulva species are rich in alkenes 95 in Okayama923 in Tokushima and 894 in Ehime prefecture Incontrast the green algae of the Monostroma species fromShizuoka prefecture contain only 63 of alkenes An oppo-site trend has been found for the relative content of aldehydesVery low relative contents are present in algae fromOkayama(02) Tokushima (01) and Ehime (01) and about 915in algae from Shizuoka prefecture
Heptadecanes derived from fatty acids were identifiedas major components among all samples 7-Heptadecane hasbeen reported to be one of the major components in marinegreen algae (Ulva pertusa and Chara vulgaris) and is knownto be the character impact compound of edible kelp It alsocontributes to the off-flavor inwater [1 19]There is a seasonalvariation in the concentration of 7-heptadecene and phytolin marine algae It was found that 7-heptadecane was usuallypresent in appreciable amounts throughout the year exceptduring summer [20]
Ketones sulfur compounds and esters occurred in sim-ilar concentration ranges in all of the samples Principalcomponent analysis was performed to identify key volatilescontributing to the flavor characteristic of the four com-mercial algae samples Figure 4 shows the correlation circleof factor 1 against factor 2 and helped us to identify majorvolatiles contributing to the distinct flavor properties of thecommercial samples
4 The Scientific World JournalTa
ble1Vo
latilec
ompo
unds
ofdifferent
greenalgaes
amples
presentedas
relativer
atiosc
omparedto
theinternalstand
ardethyldecanoate
No
Volatilec
ompo
unds
Form
ula
Class
Orig
inOdo
rdescrip
tion
RIRe
lativec
ontents(averaged
GCpeak
area
ratio
(119899=3))
Okayama
STD
Toku
shim
aST
DEh
ime
STD
Shizuo
kaST
D1
Dod
ecane
C 10H
22Alkane
Alkane(B)
1185
ND
ND
ND
1200010
2Tridecane
C 13H
28Alkane
Fatty
acids
Alkane(B)
1297
06
000
0306
000
08ND
232
00298
3226-
Trim
ethylcyclohexano
neC 9
H16O
Ketone
Caroteno
ids
Camph
oraceous
tobaccono
tes
thujon
e-lik
e(A)
1308
07
00011
07
00026
ND
ND
4Tetradecane
C 14H
30Alkane
Fatty
acids
Alkane(B)
1397
39
00020
114
000
9771
00158
60
000
655
Tetradecene
C 14H
28Alkene
1444
05
00013
09
000
0521
00025
ND
6Pentadecane
C 15H
32Alkene
Alkane(B)
1502
836
00622
2511
01181
4205
06057
ND
7(EE)-35-Octadien-2-on
eC 8
H12O
Ketone
Fatty
acids
caroteno
ids
Alm
ond(C
)1517
ND
ND
ND
ND
8Be
nzaldehyde
C 7H
5OAldehyde
Aminoacids
Sweetstr
ong
almon
d(A
)almon
dbu
rnt
sugar(B)
1517
1700028
23
000
6809
00015
37773
74504
9Pentadeceneisomer
1C 1
5H30
Alkene
1523
24
00028
36
00025
47
00057
117
00326
10Pentadeceneisomer
2C 1
5H30
Alkene
1546
07
00011
23
00025
1000010
05
00028
11Dim
ethylsulfoxide
C 2H
6OS
Sulfu
rcompo
und
Aminoacids
1557
82
00457
165
00944
80
00500
123
00221
12(EZ)-35-Octadien-2-on
eC 8
H12O
Ketone
Fatty
acids
caroteno
ids
Melo
n-lik
e(C)
1567
27
00100
21
000
6506
00052
03
00029
13Pentadeceneisomer
3C 1
5H30
Alkene
1576
ND
ND
ND
51
00085
14266-Trim
ethyl-2
-hydroxycyclohexano
neC 9
H16O
2Ke
tone
Caroteno
ids
Sweet
tobacco-lik
earom
awith
herbaceous
underton
es(A
)
1594
86
00237
9600223
41
00053
ND
15Hexadecane
C 16H
34Alkane
Alkane(B)
1601
43
00089
56
00122
7700144
282
00563
16120573-C
yclocitral
C 10H
16O
Aldehyde
Caroteno
ids
Fresh(B)
1612
35
00085
35
00074
1400010
ND
17Hexadeceneisomer
1C 1
6H32
Alkene
1619
1200010
25
00027
21
00025
ND
18Hexadeceneisomer
2C 1
6H32
Alkene
1624
09
00024
1100026
22
000
04ND
19Safranal
C 10H
14O
Aldehyde
Caroteno
ids
1637
ND
ND
ND
ND
20Heptadecane
C 17H
36Alkane
Alkane(B)
1707
561
00610
252
00936
255
02227
124
00993
217-Heptadecene
C 17H
34Alkene
1722
29097
10740
40033
33306
39543
55587
1555
03312
22Heptadecene
isomer
1C 1
7H34
Alkene
1733
1800193
ND
120
00030
7000169
23Heptadecadieneisomer
1C 1
7H32
Alkene
1757
1034
006
041392
01109
1487
01725
643
01246
24Heptadecadieneisomer
2C 1
7H32
Alkene
1766
1000021
1200018
05
000
4707
00015
25Heptadecadieneisomer
3C 1
7H32
Alkene
1769
43
00022
22
00011
08
00074
07
00104
26Heptadecadieneisomer
4C 1
7H32
Alkene
1772
38
00037
53
00036
59
000
4111
00198
27Heptadecadieneisomer
5C 1
7H32
Alkene
1779
08
00022
ND
03
00059
05
000
9128
Octadecane
C 18H
38Alkane
Alkane(B)
1801
30
00051
16000
4232
00189
21
00059
29Octadecene
C 18H
36Alkene
1817
112
00072
128
00059
181
00085
09
00081
30120572-Io
none
C 13H
20O
Ketone
Caroteno
ids
Warmw
oody
violet-floral(A
)1842
46
00039
56
00139
1800085
ND
The Scientific World Journal 5
Table1Con
tinued
No
Volatilec
ompo
unds
Form
ula
Class
Orig
inOdo
rdescrip
tion
RIRe
lativec
ontents(averaged
GCpeak
area
ratio
(119899=3))
Okayama
STD
Toku
shim
aST
DEh
ime
STD
Shizuo
kaST
D31
Non
adecane
C 19H
40Alkane
Alkane(B)
1898
29
00119
1100039
20
00029
07
00033
32120573-Io
none
C 13H
20O
Ketone
Caroteno
ids
Warmw
oody
dry(A
)1927
125
01087
157
00144
59
000
4007
00031
33Maltol
C 6H
6O3
Ketone
Caramel-
butte
rscotch(A
)caramel(B)
1960
06
00082
ND
ND
1000059
34120573-Io
none
epoxide
C 13H
20O
2Ke
tone
Caroteno
ids
Sweetb
erry
(A)
1980
21
00181
28
00025
09
000
06ND
35Methyltetradecano
ate
C 15H
30O
2Ester
Fainto
nion
ho
ney(A
)orris
(A)(B)
2010
09
00051
00
000
0013
00017
1700036
36Pentadecanal
C 15H
30O
Aldehyde
Fresh(B)
2034
1800103
31
00033
1800103
ND
3761014
-Trim
ethyl-2
-pentadecanon
eC 1
8H36O
Ketone
Caroteno
ids
2139
29
00168
67
00174
7000160
74004
27
38Hexadecanoica
cid
methyleste
rC 1
7H34O
2Ester
Fatty
acids
2217
52
00210
22
00038
9000133
22
00029
39Dihydroactin
idiolid
eC 1
1H16O
2Ke
tone
Caroteno
ids
Musky
orcoum
arin-like
(A)
2347
30
00363
84
00199
42
00022
04
00034
40Methyllinolenate
C 19H
32O
2Ester
Fatty
acids
2566
41
00390
27
000
6373
00268
34
00057
41Ph
ytol
C 20H
40O
Alcoh
olCh
loroph
yll
Faintfl
oral(A
)flo
wer
(B)
2580
28
00191
1200050
09
00023
07
00071
(A)F
oodandAgriculture
Organizationof
theu
nitednatio
ns(http
wwwfaoorg)(B)
Flavornet(httpwwwflavornetorg)and(C
)HuandPan
2000
[14]
6 The Scientific World Journal
DodecaneTridecane
Trimethylcyclohexanone
Tetradecane
TetradecenePentadecane
Benzaldehyde
Pentadecene
Pentadecene
Dimethyl sulfoxide
Pentadecene
hydroxycyclohexanone
Hexadecane
Hexadecene
Hexadecene
Safranal
Heptadecane
Heptadecene
Heptadecene
Heptadecadiene
HeptadecadieneHeptadecadiene
Heptadecadiene
Heptadecadiene
Octadecane
Octadecene
Nonadecane
Maltol
Methyl tetradecanoate
Pentadecanal
pentylidenefuran-2-one
Hexadecanoic acid methylester
Dihydroactinidiolide
Methyl linolenate
Phytol
0
025
05
075
1
025 050 075 1
minus025
minus025
minus075
minus075
minus1
minus1
minus05
minus05
120573-ionone epoxide120573-Ionone
266-Trimethyl-2-
120572-Ionone120573-Cyclocitral
35-Octadien-2-one
61014-Dimethyl
35-Octadiene-2-one
F1 (4813)
226-
Variables (axes F1 and F2 6827)F2
(20
14
)
Figure 4 Correlation circle of volatile compounds from different green algae samples The profiling was carried out based on 41 peaks anddetected corresponding peak area ratios Samples were independently analyzed in triplicate The data was analyzed by PCA using XL-STAT20132
Our analysis revealed benzaldehyde an important com-pound in algae from Shizuoka prefecture originated from theamino acid biosynthesis pathway Benzaldehyde contributesto the sweet almond odor of fruits and flowers and is char-acterized by low odor thresholds (350ndash3500 ppb) Benzalde-hyde can also be liberated from glycosidically bound precur-sors in various foods In addition it has been reported thatconcentrations increase during manufacturing processes forexample production of apple puree or roasting of sesameseeds [21]
Several hydrocarbons such as tridecane pentadecanehexadecane and dodecane were identified as relevant odorcompounds in seaweed from Shizuoka prefecture
It is noticeable that the proportion of volatile apoc-arotenoids is remarkably high in the investigated algaevarieties The importance of carotenoid-derived flavor com-pounds in algae has been previously reported Volatile apoc-arotenoids such as the potent flavor compound120573-ionone areproduced by a diversity of algae taxa for example Ulothrixfimbriata and Asakusa Nori (Porphyra tenera) [22 23] Apartfrom chemical formation pathways [24] it has been demon-strated that functional carotenoid-cleavage like enzymes
contribute to the formation of volatile apocarotenoids in algae[25]
226-Trimethylcyclohexanone (E Z)-35-octadiene-2-one 266-trimethyl-2-hydroxycyclohexa-none 120572-ionone 120573-ionone and 120573-ionone epoxide are abundant in Okayamaand Tokushima Dihydroactinidiolide makes an importantcontribution to the volatile profile of algae from TokushimaIt is also an important component in green tea with a sweetpeach-like flavor [24] In addition 120573-cyclocitral and phytolare characteristic compounds influencing the flavor of algaefrom Okayama and Tokushima prefecture they contributeto fresh and floral odors respectively [18] The ketonessuch as 120573-cyclocitral 120573-ionone and 120573-ionone epoxide andphytol are generated via degradation of carotenoids 120572-Ionone contributes to the violet wood odor 120573-ionone con-tributes to the violet-like and characteristic seaweed odor 120573-ionone epoxide contributes to the sweet berry odor Theseare important aroma impact compounds characterized byvery low odor thresholds for example 120573-ionone has an odorthreshold of 0007 ppm [26] 120573-Ionone accounts for 125157 59 and 07 of the volatiles in the algae harvestedfromOkayama Tokushima Ehime and Shizuoka prefecture
The Scientific World Journal 7
Okayama2Okayama3
Okayama1
1
Tokushima2
Tokushima1
Tokushima3
Ehime3Ehime2
Ehime1
Shizuoka2Shizuoka1
Shizuoka3
0
0
2
2
4
4
6
6
8 10minus8 minus6
minus6
minus4
minus4
minus2
minus2
Observations (axes F1 and F2 6827)
F2
(20
14
)
F1 (4813)
Figure 5 Scoring plots of nontargeted profiling of green algaesamples of different origin by GC-MS-SPME The profiling wascarried out based on 41 peaks and detected corresponding peak arearatios Samples were independently analyzed in triplicate The datawere analyzed by PCA using XL-STAT 20132
respectively Moreover thermal degradation products of120573-carotene including 226-trimethylcyclohexanone benzal-dehyde 266-trimethyl-2-hydroxycyclohexanone 120573-cyclo-citral 56-epoxy-120573-ionone and dihydroactinidiolide werepreviously reported [24]
After the removal of undesirable material green algae aresun dried and packaged It might be speculated that similarreactions occur during the sun drying processing of greenalgae and may have a strong impact on the quality of algaeproducts The occurrence of apocarotenoids is one of themost important indicators of authenticity for Ulva proliferaUlva linza andMonostroma nitidum
Another class of aroma compounds the aliphatic acidmethyl esters including hexadecanoic acid methyl esterand methyl linolenate was abundant in algae from Shizuokaprefecture Methyl linolenate serves as aprecursor of (EZ)-35-octadien-2-one and is one of the most odor-activecompounds [27] It has been found in cod liver oil and Ulvapertusa and contributes to the melon-like odor In this study(E Z)-35-octadien-2-onewas detected in all samples andwasmore abundant in Ulva prolifera
To explain the overall characteristics of the four algaesamples further studies are necessary to elucidate the con-tribution of single components and identify unknown com-pounds
Multi-variant analysis of known components was per-formed on the mass spectral data to explain the overallcharacteristics of the differences among the samples PCAwas performed using a transformed data set consisting ofcorrelation matrix of 41 variables yielding in 11 eigenvectorsFive factors explained 9239 of the total variance indicatingthat a reduced number of volatile compounds could explainthe overall characteristics of the four different samplesFactor 1 explained 4813 of the total variance and factor 2explained 2014 of the total variance Both factors together
enable discrimination of the four algae samples fromdifferentbiological and geographical origins (Figure 5) It is interestingthat there are fewer differences in the volatile profiles ofsamples from close geographic origins such as Tokushimaand Okayama compared with samples which are furtheraway from each other for example Tokushima and EhimeFuture studies should be performed with a higher number ofreplicates and taking into account testing sets
4 Conclusions
The volatile profiles of different commercial Japanese greenalgae samples originating from Okayama TokushimaEhime and Shizuoka were described for the first timeMultivariate analysis enabled discrimination of the samplesbased on their botanical and geographical origin Hithertothe authenticity of these commercial products is based onpackage information and this study could form the analyticalbasis of authenticity studies of dried green algae samplesusing the SPME-GC-MS-method followed by multivarianteanalysis
Conflict of Interests
The authors declare that there is no conflict of interests in thepaper
Acknowledgments
The authors are grateful for the gift of Monostroma nitidumfrom Kanetsu Sugiura Company Hamamatsu ShizuokaThey acknowledge the valuable discussion about the sensoryevaluation with Dr Bernhard Bruckner and thank all pan-elists for their support
References
[1] H Sugisawa K Nakamura and H Tamura ldquoThe aroma profileof the volatiles in marine green algae (Ulva pertusa)rdquo FoodReviews International vol 6 no 4 pp 573ndash589 1990
[2] S N Boopathy and K Kathiresan ldquoAnticancer drugs frommarine flora an overviewrdquo Journal of Oncology vol 2010Article ID 214186 18 pages 2010
[3] Food amp Agriculture Organization of the United Nations httpwwwfaoorgfoodfood-safety-qualityscientific-advicejecfajecfa-flaven
[4] T Kajiwara K Kodama A Hatanaka and K Matsui ldquoVolatilecompounds from Japanese marine brown algaerdquo in BioactiveVolatile Compounds from Plants vol 525 of ACS SymposiumSeries pp 103ndash120 1993
[5] Food Marketing amp Research Information Center httpwwwfmricorjptracenoriindexhtm
[6] P Poinot J Grua-Priol G Arvisenet et al ldquoOptimisation ofHS-SPME to study representativeness of partially baked breadodorant extractsrdquo Food Research International vol 40 no 9 pp1170ndash1184 2007
[7] D M A M Luykx and S M van Ruth ldquoAn overview of ana-lytical methods for determining the geographical origin of foodproductsrdquo Food Chemistry vol 107 no 2 pp 897ndash911 2008
8 The Scientific World Journal
[8] R Liu K Xiong Y Chao-Luo X Ze-Dai Z Min-Liu and WTong-Xue ldquoChanges in volatile compounds of a native Chinesechilli pepper (Capsicum frutescens var) during ripeningrdquo Inter-national Journal of Food Science amp Technology vol 44 no 12pp 2470ndash2475 2009
[9] I Silva S M Rocha and M A Coimbra ldquoHeadspace solidphase microextraction and gas chromatography-quadrupolemass spectrometry methodology for analysis of volatile com-pounds ofmarine salt as potential origin biomarkersrdquoAnalyticaChimica Acta vol 635 no 2 pp 167ndash174 2009
[10] K Tananuwong and S Lertsiri ldquoChanges in volatile aroma com-pounds of organic fragrant rice during storage under differentconditionsrdquo Journal of the Science of Food and Agriculture vol90 no 10 pp 1590ndash1596 2010
[11] K Kaseleht E Leitner and T Paalme ldquoDetermining aroma-active compounds in Kama flour using SPME-GCMS and GC-olfactometryrdquo Flavour and Fragrance Journal vol 26 no 2 pp122ndash128 2011
[12] A Prades R Assa M Dornier J P Pain and R BoulangerldquoCharacterisation of the volatile profile of coconut water fromfive varieties using an optimized HS-SPME-GC analysisrdquo Jour-nal of the Science of Food and Agriculture vol 92 pp 2471ndash24782012
[13] Flavornet httpwwwflavornetorg[14] S-P Hu and B S Pan ldquoModification of fish oil aroma using a
macroalgal lipoxygenaserdquo Journal of the American Oil ChemistsrsquoSociety vol 77 no 4 pp 343ndash348 2000
[15] Z Kamenarska A Ivanova R Stancheva et al ldquoVolatile com-pounds from some Black Sea red algae and their chemotaxo-nomic applicationrdquo Botanica Marina vol 49 no 1 pp 47ndash562006
[16] M E Hattab G Culioli L Piovetti S E Chitour and R VallsldquoComparison of various extraction methods for identificationand determination of volatile metabolites from the brown algaDictyopteris membranaceardquo Journal of Chromatography A vol1143 no 1-2 pp 1ndash7 2007
[17] V Gressler P Colepicolo and E Pinto ldquoUseful strategies foralgal volatile analysisrdquo Current Analytical Chemistry vol 5 no3 pp 271ndash292 2009
[18] R P Yu L P Wang S F Wu J S Che and Y M Liu ldquoAna-lysis of volatile compounds in Algal bloom water by gaschromatography-mass spectrometry and sniffingrdquo ChineseJournal of Analytical Chemistry vol 38 pp 1349ndash1352 2010
[19] A Rzama B Arreguy-San-Miguel and M Ettalibi ldquoLipidsmetabolites and essential oil from the green alga Chara vulgar-isrdquo Revue Marocaine des Sciences Agronomiques et Veterinairesvol 22 no 2 pp 65ndash70 2002
[20] M Okano and T Aratani ldquoConstituents in marine algae-Iseasonal variation of sterol hydrocarbon fatty acid and phytolfractions in Ulva pertusardquo Bulletin of the Japanese Society ofScientific Fisheries vol 45 pp 389ndash393 1979 (Japanese)
[21] Y H Hui Handbook of Fruit and Vegetable Flavors John Wileyamp Sons Hoboken NJ USA 2010
[22] P Fink E Von Elert and F Juttner ldquoVolatile foraging kair-omones in the littoral zone attraction of an herbivorous fresh-water gastropod to algal odorsrdquo Journal of Chemical Ecology vol32 no 9 pp 1867ndash1881 2006
[23] I Flament and G Ohloff ldquoVolatile constituents of algaeodoriferous constituents of seaweeds and structure of nor-terpenoids identified in Asakusa-Nori flavorrdquo in Proceedings ofthe 4th Weurman Flavour Research Symposium J Adda EdProgress in Flavor Research pp 281ndash300 Elsevier 1985
[24] M Kawakami ldquoIonone series compounds from beta-caroteneby thermal degradation in aqueous mediumrdquo Nippon Nogeika-gaku Kaishi vol 56 no 10 pp 917ndash921 1982 (Japanese)
[25] S Baldermann A N Mulyadi Z Yang et al ldquoApplication ofcentrifugal precipitation chromatography and high-speedcounter-current chromatography equipped with a spiral tubingsupport rotor for the isolation and partial characterization ofcarotenoid cleavage-like enzymes in Enteromorpha compressa(L) Neesrdquo Journal of Separation Science vol 34 no 19 pp2759ndash2764 2011
[26] R G Buttery R Teranishi L C Ling and J G TurnbaughldquoQuantitative and sensory studies on tomato paste volatilesrdquoJournal of Agricultural and Food Chemistry vol 38 no 1 pp336ndash340 1990
[27] F Ullrich and W Grosch ldquoIdentification of the most intenseodor compounds formed during autoxidation of methyl linole-nate at room temperaturerdquo Journal of the AmericanOil ChemistsSociety vol 65 no 8 pp 1313ndash1317 1988
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
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Organic Chemistry International
ElectrochemistryInternational Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
2 The Scientific World Journal
system such as the Food Marketing Research and Informa-tion Center in Japan [5]
GC-MS techniques coupled with multi-variant analysisare becoming increasingly important tools to monitor thedistribution of counterfeit foodstuffs and have been used inauthenticating many food products such as tea olive oilhoney cheese and wine [6ndash12]
We newly report on nontargeted SPME-GC-MS fol-lowed by multi-variant statistical analysis in Japanese greenmacroalgae Significant differences in the volatile profilesof green algae from four production areas were detectedimplying that markers could potentially be identified usingthis analytical-statistical approach
2 Experimental
21 Commercial Dried Green Algae Samples Ulva proliferaUlva linza and Monostroma nitidum commercially all soldas ldquoAonorirdquo (Japanese green algae) were subjected to sensoryevaluation and used for solid-phase microextraction (SPME)method development Ulva prolifera (2 samples) Ulva linzaand Monostroma nitidum were obtained from OkayamaTokushima Ehime and Shizuoka prefecture respectivelyCommercial Japanese green algae were purchased from awholesale agency in Japan The samples were placed in airtight plastic bags in the dark at room temperature Prior toanalysis the samples were ground to a fine powder usingliquid nitrogen
22 Sensory Evaluation The sensory tests were carried outby nine untrained panelists consuming regularly green algaeHedonic sensory attributes evaluated in this study were colortaste and overall acceptability of four green algae samplesThepanelists (6male 3 female) were between 26- and 40-yearold A nine point hedonic scale (0ndash8) anchored by dislikeextremely to like extremely for the overall score light coloredto strongly colored for the green color and weak to intensefor the taste was employedMore precisely the panelists wereasked to evaluate the following aroma attributes animalicfloral spicy fatty green note marine-like fresh (waterly)powdery and leather-like common flavor attributes of greenalgae Samples were served in glass beakers and providedrandomly to panelists Sensory evaluation procedures wereexplained to the panelists prior the tests
23 Solid Phase Microextraction (SPME) Polydimethylsilox-ane fibers (100 120583m) were mounted in a SPME manual holder(Supelco Bellefonte PA USA) All fibers were conditionedprior to analyses according to the manufacturerrsquos recom-mendations Various parameters (extraction method timeand temperature) influencing SPME analysis were optimizedFor each analysis 10 g of sample was placed in a 40 cm3 vialspiked with 1mg of the internal standard ethyldecanoateand then sealed with an aluminum crimp cap provided witha needle-pierceable polytetrafluoroethylenesilicone septumEach sample vial was placed at 50∘C for 60min to equilibrateand then the septum was pierced with the SPME needleFibers were exposed to the sample headspace for 60min
After the extraction time fibers were retracted into theneedle transferred immediately to the injection port of a GCand desorbed at 230∘C for 1min
24 GCMS Analysis The compounds collected in theheadspace above the green algae samples were analyzed byGC connected to a mass spectrometer (MS) (Shimadzu GC-MSQP5000) which was controlled by a Class-5000 worksta-tion Separation was carried out on a Supelcowax 10 fusedsilica capillary column 30m times 025mm id 025120583m filmthickness (Supelco Bellefonte PA USA) Injection was insplitless mode for 1min at 230∘C with a specific SPME insertTheGC temperaturewas raised from50 to 160∘Cat 3∘Cminminus1and from 160 to 240∘C at 10∘Cminminus1 The mass spectra werescanned at 70 eV over a mass range from mz 50 to 280Nonisothermal linear RI (Kovats type) was calculated afterthe analysis of a C11ndashC30 n-alkane series (GL Science) underthe same conditions Volatile compounds were tentativelyidentified by comparing their mass spectra with those of thereference database (NIST Mass Spectral Data 981015840 edition)Compounds were attributed to molecules through their indi-vidual mass spectrum retention indices (RI) and retentiontime (RT) In addition pure reference compounds were usedto confirm the results Flavor properties were assigned basedon reported odor descriptions [3 13 14]
25 Data Analysis The relative peak areas were calculatedin relation to the peak area of the internal standard ethylde-canoate The identified volatile compounds were classifiedinto different groups of molecules such as alkanes alkenesketones aldehydes sulfur compounds alcohols and estersUnidentified compounds were excluded from this analysisThe relative peak areas of the different compounds in eachcategory were calculated as a ratio of the total peak areaStatistical analyses were conducted using XL-STAT version2013 (Addinsoft New York USA)
3 Results and Discussion
The results of the sensory analysis revealed that it wasimpossible to differentiate between the samples based on theoverall score (Figure 1) The same applies also to taste andcolor (data not shown) Based on the nine aroma attributes(animalic floral spicy fatty green note marine-like fresh(waterly) powdery and leather-like) it was found that thesamples from Okayama Tokushima and Ehime prefectureare uniform However the sample from Shizuoka prefecturewas differently evaluated in respect of its green-note marine-like fresh and powdery aroma (Figure 2)
As a result it is impossible to distinguish between com-mercially sold ldquoAonorirdquo samples based on sensory evalua-tion Solely in taxonomically different samples OkayamaTokushima and Ehime (Ulva species) versus Shizuoka(Monostroma species) somewhat different scores could beobtained
Volatile compounds are fundamental for algae odor andaromaTherefore it is not surprising that volatile compoundsin algae have been investigated and reports evaluating volatile
The Scientific World Journal 3
Okayama EhimeTokushima0
2
4
6
8
Scor
e
Shizuoka
Figure 1 Overall scores of the sensory evaluation of green algaesamples
001020304050607080Animalic
Floral
Spicy
Fatty
Green noteMarine-like
Fresh
Powderly
Leather-like
OkayamaTokushima
EhimeShizuoka
Figure 2 Sensory characterisation of green algae samples Thefollowing aroma attributes were determined based on panelistrsquosevaluation animalic floral spicy fatty green note marine-likefresh (waterly) powdery and leather-like
metabolites for example in brown and red algae are availablein the current literature [15ndash18]
GC-MS techniques coupled with multi-variant analysishave been used in authenticating many food products andshould be tested in this study for its practicability to dis-tinguish different commercially sold Japanese green algaesamples
Forty-one major volatile compounds classed as alkanesalkenes ketones aldehydes sulfur compounds alcoholsand esters were identified in the four commercial Japanesegreen algae (Table 1) These compounds are derived from
00
200
400
600
800
1000Alkanes
Alkenes
Ketones
AldehydesSulfur compounds
Alcohols
Esters
OkayamaTokushima
EhimeShizuoka
Figure 3 Chemical classification of volatile compounds in relativeconcentrations (119899 = 3) in different commercial green algae samples
different precursors including the amino acids fatty acidsand carotenoids (Table 1)
Hydrocarbons including alkanes and alkenes (eg tetra-decene pentadecane hexadecane and octadecene) wereabundant in three (Okayama Tokushima and Ehime) of thefour samples (Figure 3)
The relative concentrations of alkenes vary among thesamples from different algae of the orderUlvales Green algaeof the Ulva species are rich in alkenes 95 in Okayama923 in Tokushima and 894 in Ehime prefecture Incontrast the green algae of the Monostroma species fromShizuoka prefecture contain only 63 of alkenes An oppo-site trend has been found for the relative content of aldehydesVery low relative contents are present in algae fromOkayama(02) Tokushima (01) and Ehime (01) and about 915in algae from Shizuoka prefecture
Heptadecanes derived from fatty acids were identifiedas major components among all samples 7-Heptadecane hasbeen reported to be one of the major components in marinegreen algae (Ulva pertusa and Chara vulgaris) and is knownto be the character impact compound of edible kelp It alsocontributes to the off-flavor inwater [1 19]There is a seasonalvariation in the concentration of 7-heptadecene and phytolin marine algae It was found that 7-heptadecane was usuallypresent in appreciable amounts throughout the year exceptduring summer [20]
Ketones sulfur compounds and esters occurred in sim-ilar concentration ranges in all of the samples Principalcomponent analysis was performed to identify key volatilescontributing to the flavor characteristic of the four com-mercial algae samples Figure 4 shows the correlation circleof factor 1 against factor 2 and helped us to identify majorvolatiles contributing to the distinct flavor properties of thecommercial samples
4 The Scientific World JournalTa
ble1Vo
latilec
ompo
unds
ofdifferent
greenalgaes
amples
presentedas
relativer
atiosc
omparedto
theinternalstand
ardethyldecanoate
No
Volatilec
ompo
unds
Form
ula
Class
Orig
inOdo
rdescrip
tion
RIRe
lativec
ontents(averaged
GCpeak
area
ratio
(119899=3))
Okayama
STD
Toku
shim
aST
DEh
ime
STD
Shizuo
kaST
D1
Dod
ecane
C 10H
22Alkane
Alkane(B)
1185
ND
ND
ND
1200010
2Tridecane
C 13H
28Alkane
Fatty
acids
Alkane(B)
1297
06
000
0306
000
08ND
232
00298
3226-
Trim
ethylcyclohexano
neC 9
H16O
Ketone
Caroteno
ids
Camph
oraceous
tobaccono
tes
thujon
e-lik
e(A)
1308
07
00011
07
00026
ND
ND
4Tetradecane
C 14H
30Alkane
Fatty
acids
Alkane(B)
1397
39
00020
114
000
9771
00158
60
000
655
Tetradecene
C 14H
28Alkene
1444
05
00013
09
000
0521
00025
ND
6Pentadecane
C 15H
32Alkene
Alkane(B)
1502
836
00622
2511
01181
4205
06057
ND
7(EE)-35-Octadien-2-on
eC 8
H12O
Ketone
Fatty
acids
caroteno
ids
Alm
ond(C
)1517
ND
ND
ND
ND
8Be
nzaldehyde
C 7H
5OAldehyde
Aminoacids
Sweetstr
ong
almon
d(A
)almon
dbu
rnt
sugar(B)
1517
1700028
23
000
6809
00015
37773
74504
9Pentadeceneisomer
1C 1
5H30
Alkene
1523
24
00028
36
00025
47
00057
117
00326
10Pentadeceneisomer
2C 1
5H30
Alkene
1546
07
00011
23
00025
1000010
05
00028
11Dim
ethylsulfoxide
C 2H
6OS
Sulfu
rcompo
und
Aminoacids
1557
82
00457
165
00944
80
00500
123
00221
12(EZ)-35-Octadien-2-on
eC 8
H12O
Ketone
Fatty
acids
caroteno
ids
Melo
n-lik
e(C)
1567
27
00100
21
000
6506
00052
03
00029
13Pentadeceneisomer
3C 1
5H30
Alkene
1576
ND
ND
ND
51
00085
14266-Trim
ethyl-2
-hydroxycyclohexano
neC 9
H16O
2Ke
tone
Caroteno
ids
Sweet
tobacco-lik
earom
awith
herbaceous
underton
es(A
)
1594
86
00237
9600223
41
00053
ND
15Hexadecane
C 16H
34Alkane
Alkane(B)
1601
43
00089
56
00122
7700144
282
00563
16120573-C
yclocitral
C 10H
16O
Aldehyde
Caroteno
ids
Fresh(B)
1612
35
00085
35
00074
1400010
ND
17Hexadeceneisomer
1C 1
6H32
Alkene
1619
1200010
25
00027
21
00025
ND
18Hexadeceneisomer
2C 1
6H32
Alkene
1624
09
00024
1100026
22
000
04ND
19Safranal
C 10H
14O
Aldehyde
Caroteno
ids
1637
ND
ND
ND
ND
20Heptadecane
C 17H
36Alkane
Alkane(B)
1707
561
00610
252
00936
255
02227
124
00993
217-Heptadecene
C 17H
34Alkene
1722
29097
10740
40033
33306
39543
55587
1555
03312
22Heptadecene
isomer
1C 1
7H34
Alkene
1733
1800193
ND
120
00030
7000169
23Heptadecadieneisomer
1C 1
7H32
Alkene
1757
1034
006
041392
01109
1487
01725
643
01246
24Heptadecadieneisomer
2C 1
7H32
Alkene
1766
1000021
1200018
05
000
4707
00015
25Heptadecadieneisomer
3C 1
7H32
Alkene
1769
43
00022
22
00011
08
00074
07
00104
26Heptadecadieneisomer
4C 1
7H32
Alkene
1772
38
00037
53
00036
59
000
4111
00198
27Heptadecadieneisomer
5C 1
7H32
Alkene
1779
08
00022
ND
03
00059
05
000
9128
Octadecane
C 18H
38Alkane
Alkane(B)
1801
30
00051
16000
4232
00189
21
00059
29Octadecene
C 18H
36Alkene
1817
112
00072
128
00059
181
00085
09
00081
30120572-Io
none
C 13H
20O
Ketone
Caroteno
ids
Warmw
oody
violet-floral(A
)1842
46
00039
56
00139
1800085
ND
The Scientific World Journal 5
Table1Con
tinued
No
Volatilec
ompo
unds
Form
ula
Class
Orig
inOdo
rdescrip
tion
RIRe
lativec
ontents(averaged
GCpeak
area
ratio
(119899=3))
Okayama
STD
Toku
shim
aST
DEh
ime
STD
Shizuo
kaST
D31
Non
adecane
C 19H
40Alkane
Alkane(B)
1898
29
00119
1100039
20
00029
07
00033
32120573-Io
none
C 13H
20O
Ketone
Caroteno
ids
Warmw
oody
dry(A
)1927
125
01087
157
00144
59
000
4007
00031
33Maltol
C 6H
6O3
Ketone
Caramel-
butte
rscotch(A
)caramel(B)
1960
06
00082
ND
ND
1000059
34120573-Io
none
epoxide
C 13H
20O
2Ke
tone
Caroteno
ids
Sweetb
erry
(A)
1980
21
00181
28
00025
09
000
06ND
35Methyltetradecano
ate
C 15H
30O
2Ester
Fainto
nion
ho
ney(A
)orris
(A)(B)
2010
09
00051
00
000
0013
00017
1700036
36Pentadecanal
C 15H
30O
Aldehyde
Fresh(B)
2034
1800103
31
00033
1800103
ND
3761014
-Trim
ethyl-2
-pentadecanon
eC 1
8H36O
Ketone
Caroteno
ids
2139
29
00168
67
00174
7000160
74004
27
38Hexadecanoica
cid
methyleste
rC 1
7H34O
2Ester
Fatty
acids
2217
52
00210
22
00038
9000133
22
00029
39Dihydroactin
idiolid
eC 1
1H16O
2Ke
tone
Caroteno
ids
Musky
orcoum
arin-like
(A)
2347
30
00363
84
00199
42
00022
04
00034
40Methyllinolenate
C 19H
32O
2Ester
Fatty
acids
2566
41
00390
27
000
6373
00268
34
00057
41Ph
ytol
C 20H
40O
Alcoh
olCh
loroph
yll
Faintfl
oral(A
)flo
wer
(B)
2580
28
00191
1200050
09
00023
07
00071
(A)F
oodandAgriculture
Organizationof
theu
nitednatio
ns(http
wwwfaoorg)(B)
Flavornet(httpwwwflavornetorg)and(C
)HuandPan
2000
[14]
6 The Scientific World Journal
DodecaneTridecane
Trimethylcyclohexanone
Tetradecane
TetradecenePentadecane
Benzaldehyde
Pentadecene
Pentadecene
Dimethyl sulfoxide
Pentadecene
hydroxycyclohexanone
Hexadecane
Hexadecene
Hexadecene
Safranal
Heptadecane
Heptadecene
Heptadecene
Heptadecadiene
HeptadecadieneHeptadecadiene
Heptadecadiene
Heptadecadiene
Octadecane
Octadecene
Nonadecane
Maltol
Methyl tetradecanoate
Pentadecanal
pentylidenefuran-2-one
Hexadecanoic acid methylester
Dihydroactinidiolide
Methyl linolenate
Phytol
0
025
05
075
1
025 050 075 1
minus025
minus025
minus075
minus075
minus1
minus1
minus05
minus05
120573-ionone epoxide120573-Ionone
266-Trimethyl-2-
120572-Ionone120573-Cyclocitral
35-Octadien-2-one
61014-Dimethyl
35-Octadiene-2-one
F1 (4813)
226-
Variables (axes F1 and F2 6827)F2
(20
14
)
Figure 4 Correlation circle of volatile compounds from different green algae samples The profiling was carried out based on 41 peaks anddetected corresponding peak area ratios Samples were independently analyzed in triplicate The data was analyzed by PCA using XL-STAT20132
Our analysis revealed benzaldehyde an important com-pound in algae from Shizuoka prefecture originated from theamino acid biosynthesis pathway Benzaldehyde contributesto the sweet almond odor of fruits and flowers and is char-acterized by low odor thresholds (350ndash3500 ppb) Benzalde-hyde can also be liberated from glycosidically bound precur-sors in various foods In addition it has been reported thatconcentrations increase during manufacturing processes forexample production of apple puree or roasting of sesameseeds [21]
Several hydrocarbons such as tridecane pentadecanehexadecane and dodecane were identified as relevant odorcompounds in seaweed from Shizuoka prefecture
It is noticeable that the proportion of volatile apoc-arotenoids is remarkably high in the investigated algaevarieties The importance of carotenoid-derived flavor com-pounds in algae has been previously reported Volatile apoc-arotenoids such as the potent flavor compound120573-ionone areproduced by a diversity of algae taxa for example Ulothrixfimbriata and Asakusa Nori (Porphyra tenera) [22 23] Apartfrom chemical formation pathways [24] it has been demon-strated that functional carotenoid-cleavage like enzymes
contribute to the formation of volatile apocarotenoids in algae[25]
226-Trimethylcyclohexanone (E Z)-35-octadiene-2-one 266-trimethyl-2-hydroxycyclohexa-none 120572-ionone 120573-ionone and 120573-ionone epoxide are abundant in Okayamaand Tokushima Dihydroactinidiolide makes an importantcontribution to the volatile profile of algae from TokushimaIt is also an important component in green tea with a sweetpeach-like flavor [24] In addition 120573-cyclocitral and phytolare characteristic compounds influencing the flavor of algaefrom Okayama and Tokushima prefecture they contributeto fresh and floral odors respectively [18] The ketonessuch as 120573-cyclocitral 120573-ionone and 120573-ionone epoxide andphytol are generated via degradation of carotenoids 120572-Ionone contributes to the violet wood odor 120573-ionone con-tributes to the violet-like and characteristic seaweed odor 120573-ionone epoxide contributes to the sweet berry odor Theseare important aroma impact compounds characterized byvery low odor thresholds for example 120573-ionone has an odorthreshold of 0007 ppm [26] 120573-Ionone accounts for 125157 59 and 07 of the volatiles in the algae harvestedfromOkayama Tokushima Ehime and Shizuoka prefecture
The Scientific World Journal 7
Okayama2Okayama3
Okayama1
1
Tokushima2
Tokushima1
Tokushima3
Ehime3Ehime2
Ehime1
Shizuoka2Shizuoka1
Shizuoka3
0
0
2
2
4
4
6
6
8 10minus8 minus6
minus6
minus4
minus4
minus2
minus2
Observations (axes F1 and F2 6827)
F2
(20
14
)
F1 (4813)
Figure 5 Scoring plots of nontargeted profiling of green algaesamples of different origin by GC-MS-SPME The profiling wascarried out based on 41 peaks and detected corresponding peak arearatios Samples were independently analyzed in triplicate The datawere analyzed by PCA using XL-STAT 20132
respectively Moreover thermal degradation products of120573-carotene including 226-trimethylcyclohexanone benzal-dehyde 266-trimethyl-2-hydroxycyclohexanone 120573-cyclo-citral 56-epoxy-120573-ionone and dihydroactinidiolide werepreviously reported [24]
After the removal of undesirable material green algae aresun dried and packaged It might be speculated that similarreactions occur during the sun drying processing of greenalgae and may have a strong impact on the quality of algaeproducts The occurrence of apocarotenoids is one of themost important indicators of authenticity for Ulva proliferaUlva linza andMonostroma nitidum
Another class of aroma compounds the aliphatic acidmethyl esters including hexadecanoic acid methyl esterand methyl linolenate was abundant in algae from Shizuokaprefecture Methyl linolenate serves as aprecursor of (EZ)-35-octadien-2-one and is one of the most odor-activecompounds [27] It has been found in cod liver oil and Ulvapertusa and contributes to the melon-like odor In this study(E Z)-35-octadien-2-onewas detected in all samples andwasmore abundant in Ulva prolifera
To explain the overall characteristics of the four algaesamples further studies are necessary to elucidate the con-tribution of single components and identify unknown com-pounds
Multi-variant analysis of known components was per-formed on the mass spectral data to explain the overallcharacteristics of the differences among the samples PCAwas performed using a transformed data set consisting ofcorrelation matrix of 41 variables yielding in 11 eigenvectorsFive factors explained 9239 of the total variance indicatingthat a reduced number of volatile compounds could explainthe overall characteristics of the four different samplesFactor 1 explained 4813 of the total variance and factor 2explained 2014 of the total variance Both factors together
enable discrimination of the four algae samples fromdifferentbiological and geographical origins (Figure 5) It is interestingthat there are fewer differences in the volatile profiles ofsamples from close geographic origins such as Tokushimaand Okayama compared with samples which are furtheraway from each other for example Tokushima and EhimeFuture studies should be performed with a higher number ofreplicates and taking into account testing sets
4 Conclusions
The volatile profiles of different commercial Japanese greenalgae samples originating from Okayama TokushimaEhime and Shizuoka were described for the first timeMultivariate analysis enabled discrimination of the samplesbased on their botanical and geographical origin Hithertothe authenticity of these commercial products is based onpackage information and this study could form the analyticalbasis of authenticity studies of dried green algae samplesusing the SPME-GC-MS-method followed by multivarianteanalysis
Conflict of Interests
The authors declare that there is no conflict of interests in thepaper
Acknowledgments
The authors are grateful for the gift of Monostroma nitidumfrom Kanetsu Sugiura Company Hamamatsu ShizuokaThey acknowledge the valuable discussion about the sensoryevaluation with Dr Bernhard Bruckner and thank all pan-elists for their support
References
[1] H Sugisawa K Nakamura and H Tamura ldquoThe aroma profileof the volatiles in marine green algae (Ulva pertusa)rdquo FoodReviews International vol 6 no 4 pp 573ndash589 1990
[2] S N Boopathy and K Kathiresan ldquoAnticancer drugs frommarine flora an overviewrdquo Journal of Oncology vol 2010Article ID 214186 18 pages 2010
[3] Food amp Agriculture Organization of the United Nations httpwwwfaoorgfoodfood-safety-qualityscientific-advicejecfajecfa-flaven
[4] T Kajiwara K Kodama A Hatanaka and K Matsui ldquoVolatilecompounds from Japanese marine brown algaerdquo in BioactiveVolatile Compounds from Plants vol 525 of ACS SymposiumSeries pp 103ndash120 1993
[5] Food Marketing amp Research Information Center httpwwwfmricorjptracenoriindexhtm
[6] P Poinot J Grua-Priol G Arvisenet et al ldquoOptimisation ofHS-SPME to study representativeness of partially baked breadodorant extractsrdquo Food Research International vol 40 no 9 pp1170ndash1184 2007
[7] D M A M Luykx and S M van Ruth ldquoAn overview of ana-lytical methods for determining the geographical origin of foodproductsrdquo Food Chemistry vol 107 no 2 pp 897ndash911 2008
8 The Scientific World Journal
[8] R Liu K Xiong Y Chao-Luo X Ze-Dai Z Min-Liu and WTong-Xue ldquoChanges in volatile compounds of a native Chinesechilli pepper (Capsicum frutescens var) during ripeningrdquo Inter-national Journal of Food Science amp Technology vol 44 no 12pp 2470ndash2475 2009
[9] I Silva S M Rocha and M A Coimbra ldquoHeadspace solidphase microextraction and gas chromatography-quadrupolemass spectrometry methodology for analysis of volatile com-pounds ofmarine salt as potential origin biomarkersrdquoAnalyticaChimica Acta vol 635 no 2 pp 167ndash174 2009
[10] K Tananuwong and S Lertsiri ldquoChanges in volatile aroma com-pounds of organic fragrant rice during storage under differentconditionsrdquo Journal of the Science of Food and Agriculture vol90 no 10 pp 1590ndash1596 2010
[11] K Kaseleht E Leitner and T Paalme ldquoDetermining aroma-active compounds in Kama flour using SPME-GCMS and GC-olfactometryrdquo Flavour and Fragrance Journal vol 26 no 2 pp122ndash128 2011
[12] A Prades R Assa M Dornier J P Pain and R BoulangerldquoCharacterisation of the volatile profile of coconut water fromfive varieties using an optimized HS-SPME-GC analysisrdquo Jour-nal of the Science of Food and Agriculture vol 92 pp 2471ndash24782012
[13] Flavornet httpwwwflavornetorg[14] S-P Hu and B S Pan ldquoModification of fish oil aroma using a
macroalgal lipoxygenaserdquo Journal of the American Oil ChemistsrsquoSociety vol 77 no 4 pp 343ndash348 2000
[15] Z Kamenarska A Ivanova R Stancheva et al ldquoVolatile com-pounds from some Black Sea red algae and their chemotaxo-nomic applicationrdquo Botanica Marina vol 49 no 1 pp 47ndash562006
[16] M E Hattab G Culioli L Piovetti S E Chitour and R VallsldquoComparison of various extraction methods for identificationand determination of volatile metabolites from the brown algaDictyopteris membranaceardquo Journal of Chromatography A vol1143 no 1-2 pp 1ndash7 2007
[17] V Gressler P Colepicolo and E Pinto ldquoUseful strategies foralgal volatile analysisrdquo Current Analytical Chemistry vol 5 no3 pp 271ndash292 2009
[18] R P Yu L P Wang S F Wu J S Che and Y M Liu ldquoAna-lysis of volatile compounds in Algal bloom water by gaschromatography-mass spectrometry and sniffingrdquo ChineseJournal of Analytical Chemistry vol 38 pp 1349ndash1352 2010
[19] A Rzama B Arreguy-San-Miguel and M Ettalibi ldquoLipidsmetabolites and essential oil from the green alga Chara vulgar-isrdquo Revue Marocaine des Sciences Agronomiques et Veterinairesvol 22 no 2 pp 65ndash70 2002
[20] M Okano and T Aratani ldquoConstituents in marine algae-Iseasonal variation of sterol hydrocarbon fatty acid and phytolfractions in Ulva pertusardquo Bulletin of the Japanese Society ofScientific Fisheries vol 45 pp 389ndash393 1979 (Japanese)
[21] Y H Hui Handbook of Fruit and Vegetable Flavors John Wileyamp Sons Hoboken NJ USA 2010
[22] P Fink E Von Elert and F Juttner ldquoVolatile foraging kair-omones in the littoral zone attraction of an herbivorous fresh-water gastropod to algal odorsrdquo Journal of Chemical Ecology vol32 no 9 pp 1867ndash1881 2006
[23] I Flament and G Ohloff ldquoVolatile constituents of algaeodoriferous constituents of seaweeds and structure of nor-terpenoids identified in Asakusa-Nori flavorrdquo in Proceedings ofthe 4th Weurman Flavour Research Symposium J Adda EdProgress in Flavor Research pp 281ndash300 Elsevier 1985
[24] M Kawakami ldquoIonone series compounds from beta-caroteneby thermal degradation in aqueous mediumrdquo Nippon Nogeika-gaku Kaishi vol 56 no 10 pp 917ndash921 1982 (Japanese)
[25] S Baldermann A N Mulyadi Z Yang et al ldquoApplication ofcentrifugal precipitation chromatography and high-speedcounter-current chromatography equipped with a spiral tubingsupport rotor for the isolation and partial characterization ofcarotenoid cleavage-like enzymes in Enteromorpha compressa(L) Neesrdquo Journal of Separation Science vol 34 no 19 pp2759ndash2764 2011
[26] R G Buttery R Teranishi L C Ling and J G TurnbaughldquoQuantitative and sensory studies on tomato paste volatilesrdquoJournal of Agricultural and Food Chemistry vol 38 no 1 pp336ndash340 1990
[27] F Ullrich and W Grosch ldquoIdentification of the most intenseodor compounds formed during autoxidation of methyl linole-nate at room temperaturerdquo Journal of the AmericanOil ChemistsSociety vol 65 no 8 pp 1313ndash1317 1988
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
The Scientific World Journal 3
Okayama EhimeTokushima0
2
4
6
8
Scor
e
Shizuoka
Figure 1 Overall scores of the sensory evaluation of green algaesamples
001020304050607080Animalic
Floral
Spicy
Fatty
Green noteMarine-like
Fresh
Powderly
Leather-like
OkayamaTokushima
EhimeShizuoka
Figure 2 Sensory characterisation of green algae samples Thefollowing aroma attributes were determined based on panelistrsquosevaluation animalic floral spicy fatty green note marine-likefresh (waterly) powdery and leather-like
metabolites for example in brown and red algae are availablein the current literature [15ndash18]
GC-MS techniques coupled with multi-variant analysishave been used in authenticating many food products andshould be tested in this study for its practicability to dis-tinguish different commercially sold Japanese green algaesamples
Forty-one major volatile compounds classed as alkanesalkenes ketones aldehydes sulfur compounds alcoholsand esters were identified in the four commercial Japanesegreen algae (Table 1) These compounds are derived from
00
200
400
600
800
1000Alkanes
Alkenes
Ketones
AldehydesSulfur compounds
Alcohols
Esters
OkayamaTokushima
EhimeShizuoka
Figure 3 Chemical classification of volatile compounds in relativeconcentrations (119899 = 3) in different commercial green algae samples
different precursors including the amino acids fatty acidsand carotenoids (Table 1)
Hydrocarbons including alkanes and alkenes (eg tetra-decene pentadecane hexadecane and octadecene) wereabundant in three (Okayama Tokushima and Ehime) of thefour samples (Figure 3)
The relative concentrations of alkenes vary among thesamples from different algae of the orderUlvales Green algaeof the Ulva species are rich in alkenes 95 in Okayama923 in Tokushima and 894 in Ehime prefecture Incontrast the green algae of the Monostroma species fromShizuoka prefecture contain only 63 of alkenes An oppo-site trend has been found for the relative content of aldehydesVery low relative contents are present in algae fromOkayama(02) Tokushima (01) and Ehime (01) and about 915in algae from Shizuoka prefecture
Heptadecanes derived from fatty acids were identifiedas major components among all samples 7-Heptadecane hasbeen reported to be one of the major components in marinegreen algae (Ulva pertusa and Chara vulgaris) and is knownto be the character impact compound of edible kelp It alsocontributes to the off-flavor inwater [1 19]There is a seasonalvariation in the concentration of 7-heptadecene and phytolin marine algae It was found that 7-heptadecane was usuallypresent in appreciable amounts throughout the year exceptduring summer [20]
Ketones sulfur compounds and esters occurred in sim-ilar concentration ranges in all of the samples Principalcomponent analysis was performed to identify key volatilescontributing to the flavor characteristic of the four com-mercial algae samples Figure 4 shows the correlation circleof factor 1 against factor 2 and helped us to identify majorvolatiles contributing to the distinct flavor properties of thecommercial samples
4 The Scientific World JournalTa
ble1Vo
latilec
ompo
unds
ofdifferent
greenalgaes
amples
presentedas
relativer
atiosc
omparedto
theinternalstand
ardethyldecanoate
No
Volatilec
ompo
unds
Form
ula
Class
Orig
inOdo
rdescrip
tion
RIRe
lativec
ontents(averaged
GCpeak
area
ratio
(119899=3))
Okayama
STD
Toku
shim
aST
DEh
ime
STD
Shizuo
kaST
D1
Dod
ecane
C 10H
22Alkane
Alkane(B)
1185
ND
ND
ND
1200010
2Tridecane
C 13H
28Alkane
Fatty
acids
Alkane(B)
1297
06
000
0306
000
08ND
232
00298
3226-
Trim
ethylcyclohexano
neC 9
H16O
Ketone
Caroteno
ids
Camph
oraceous
tobaccono
tes
thujon
e-lik
e(A)
1308
07
00011
07
00026
ND
ND
4Tetradecane
C 14H
30Alkane
Fatty
acids
Alkane(B)
1397
39
00020
114
000
9771
00158
60
000
655
Tetradecene
C 14H
28Alkene
1444
05
00013
09
000
0521
00025
ND
6Pentadecane
C 15H
32Alkene
Alkane(B)
1502
836
00622
2511
01181
4205
06057
ND
7(EE)-35-Octadien-2-on
eC 8
H12O
Ketone
Fatty
acids
caroteno
ids
Alm
ond(C
)1517
ND
ND
ND
ND
8Be
nzaldehyde
C 7H
5OAldehyde
Aminoacids
Sweetstr
ong
almon
d(A
)almon
dbu
rnt
sugar(B)
1517
1700028
23
000
6809
00015
37773
74504
9Pentadeceneisomer
1C 1
5H30
Alkene
1523
24
00028
36
00025
47
00057
117
00326
10Pentadeceneisomer
2C 1
5H30
Alkene
1546
07
00011
23
00025
1000010
05
00028
11Dim
ethylsulfoxide
C 2H
6OS
Sulfu
rcompo
und
Aminoacids
1557
82
00457
165
00944
80
00500
123
00221
12(EZ)-35-Octadien-2-on
eC 8
H12O
Ketone
Fatty
acids
caroteno
ids
Melo
n-lik
e(C)
1567
27
00100
21
000
6506
00052
03
00029
13Pentadeceneisomer
3C 1
5H30
Alkene
1576
ND
ND
ND
51
00085
14266-Trim
ethyl-2
-hydroxycyclohexano
neC 9
H16O
2Ke
tone
Caroteno
ids
Sweet
tobacco-lik
earom
awith
herbaceous
underton
es(A
)
1594
86
00237
9600223
41
00053
ND
15Hexadecane
C 16H
34Alkane
Alkane(B)
1601
43
00089
56
00122
7700144
282
00563
16120573-C
yclocitral
C 10H
16O
Aldehyde
Caroteno
ids
Fresh(B)
1612
35
00085
35
00074
1400010
ND
17Hexadeceneisomer
1C 1
6H32
Alkene
1619
1200010
25
00027
21
00025
ND
18Hexadeceneisomer
2C 1
6H32
Alkene
1624
09
00024
1100026
22
000
04ND
19Safranal
C 10H
14O
Aldehyde
Caroteno
ids
1637
ND
ND
ND
ND
20Heptadecane
C 17H
36Alkane
Alkane(B)
1707
561
00610
252
00936
255
02227
124
00993
217-Heptadecene
C 17H
34Alkene
1722
29097
10740
40033
33306
39543
55587
1555
03312
22Heptadecene
isomer
1C 1
7H34
Alkene
1733
1800193
ND
120
00030
7000169
23Heptadecadieneisomer
1C 1
7H32
Alkene
1757
1034
006
041392
01109
1487
01725
643
01246
24Heptadecadieneisomer
2C 1
7H32
Alkene
1766
1000021
1200018
05
000
4707
00015
25Heptadecadieneisomer
3C 1
7H32
Alkene
1769
43
00022
22
00011
08
00074
07
00104
26Heptadecadieneisomer
4C 1
7H32
Alkene
1772
38
00037
53
00036
59
000
4111
00198
27Heptadecadieneisomer
5C 1
7H32
Alkene
1779
08
00022
ND
03
00059
05
000
9128
Octadecane
C 18H
38Alkane
Alkane(B)
1801
30
00051
16000
4232
00189
21
00059
29Octadecene
C 18H
36Alkene
1817
112
00072
128
00059
181
00085
09
00081
30120572-Io
none
C 13H
20O
Ketone
Caroteno
ids
Warmw
oody
violet-floral(A
)1842
46
00039
56
00139
1800085
ND
The Scientific World Journal 5
Table1Con
tinued
No
Volatilec
ompo
unds
Form
ula
Class
Orig
inOdo
rdescrip
tion
RIRe
lativec
ontents(averaged
GCpeak
area
ratio
(119899=3))
Okayama
STD
Toku
shim
aST
DEh
ime
STD
Shizuo
kaST
D31
Non
adecane
C 19H
40Alkane
Alkane(B)
1898
29
00119
1100039
20
00029
07
00033
32120573-Io
none
C 13H
20O
Ketone
Caroteno
ids
Warmw
oody
dry(A
)1927
125
01087
157
00144
59
000
4007
00031
33Maltol
C 6H
6O3
Ketone
Caramel-
butte
rscotch(A
)caramel(B)
1960
06
00082
ND
ND
1000059
34120573-Io
none
epoxide
C 13H
20O
2Ke
tone
Caroteno
ids
Sweetb
erry
(A)
1980
21
00181
28
00025
09
000
06ND
35Methyltetradecano
ate
C 15H
30O
2Ester
Fainto
nion
ho
ney(A
)orris
(A)(B)
2010
09
00051
00
000
0013
00017
1700036
36Pentadecanal
C 15H
30O
Aldehyde
Fresh(B)
2034
1800103
31
00033
1800103
ND
3761014
-Trim
ethyl-2
-pentadecanon
eC 1
8H36O
Ketone
Caroteno
ids
2139
29
00168
67
00174
7000160
74004
27
38Hexadecanoica
cid
methyleste
rC 1
7H34O
2Ester
Fatty
acids
2217
52
00210
22
00038
9000133
22
00029
39Dihydroactin
idiolid
eC 1
1H16O
2Ke
tone
Caroteno
ids
Musky
orcoum
arin-like
(A)
2347
30
00363
84
00199
42
00022
04
00034
40Methyllinolenate
C 19H
32O
2Ester
Fatty
acids
2566
41
00390
27
000
6373
00268
34
00057
41Ph
ytol
C 20H
40O
Alcoh
olCh
loroph
yll
Faintfl
oral(A
)flo
wer
(B)
2580
28
00191
1200050
09
00023
07
00071
(A)F
oodandAgriculture
Organizationof
theu
nitednatio
ns(http
wwwfaoorg)(B)
Flavornet(httpwwwflavornetorg)and(C
)HuandPan
2000
[14]
6 The Scientific World Journal
DodecaneTridecane
Trimethylcyclohexanone
Tetradecane
TetradecenePentadecane
Benzaldehyde
Pentadecene
Pentadecene
Dimethyl sulfoxide
Pentadecene
hydroxycyclohexanone
Hexadecane
Hexadecene
Hexadecene
Safranal
Heptadecane
Heptadecene
Heptadecene
Heptadecadiene
HeptadecadieneHeptadecadiene
Heptadecadiene
Heptadecadiene
Octadecane
Octadecene
Nonadecane
Maltol
Methyl tetradecanoate
Pentadecanal
pentylidenefuran-2-one
Hexadecanoic acid methylester
Dihydroactinidiolide
Methyl linolenate
Phytol
0
025
05
075
1
025 050 075 1
minus025
minus025
minus075
minus075
minus1
minus1
minus05
minus05
120573-ionone epoxide120573-Ionone
266-Trimethyl-2-
120572-Ionone120573-Cyclocitral
35-Octadien-2-one
61014-Dimethyl
35-Octadiene-2-one
F1 (4813)
226-
Variables (axes F1 and F2 6827)F2
(20
14
)
Figure 4 Correlation circle of volatile compounds from different green algae samples The profiling was carried out based on 41 peaks anddetected corresponding peak area ratios Samples were independently analyzed in triplicate The data was analyzed by PCA using XL-STAT20132
Our analysis revealed benzaldehyde an important com-pound in algae from Shizuoka prefecture originated from theamino acid biosynthesis pathway Benzaldehyde contributesto the sweet almond odor of fruits and flowers and is char-acterized by low odor thresholds (350ndash3500 ppb) Benzalde-hyde can also be liberated from glycosidically bound precur-sors in various foods In addition it has been reported thatconcentrations increase during manufacturing processes forexample production of apple puree or roasting of sesameseeds [21]
Several hydrocarbons such as tridecane pentadecanehexadecane and dodecane were identified as relevant odorcompounds in seaweed from Shizuoka prefecture
It is noticeable that the proportion of volatile apoc-arotenoids is remarkably high in the investigated algaevarieties The importance of carotenoid-derived flavor com-pounds in algae has been previously reported Volatile apoc-arotenoids such as the potent flavor compound120573-ionone areproduced by a diversity of algae taxa for example Ulothrixfimbriata and Asakusa Nori (Porphyra tenera) [22 23] Apartfrom chemical formation pathways [24] it has been demon-strated that functional carotenoid-cleavage like enzymes
contribute to the formation of volatile apocarotenoids in algae[25]
226-Trimethylcyclohexanone (E Z)-35-octadiene-2-one 266-trimethyl-2-hydroxycyclohexa-none 120572-ionone 120573-ionone and 120573-ionone epoxide are abundant in Okayamaand Tokushima Dihydroactinidiolide makes an importantcontribution to the volatile profile of algae from TokushimaIt is also an important component in green tea with a sweetpeach-like flavor [24] In addition 120573-cyclocitral and phytolare characteristic compounds influencing the flavor of algaefrom Okayama and Tokushima prefecture they contributeto fresh and floral odors respectively [18] The ketonessuch as 120573-cyclocitral 120573-ionone and 120573-ionone epoxide andphytol are generated via degradation of carotenoids 120572-Ionone contributes to the violet wood odor 120573-ionone con-tributes to the violet-like and characteristic seaweed odor 120573-ionone epoxide contributes to the sweet berry odor Theseare important aroma impact compounds characterized byvery low odor thresholds for example 120573-ionone has an odorthreshold of 0007 ppm [26] 120573-Ionone accounts for 125157 59 and 07 of the volatiles in the algae harvestedfromOkayama Tokushima Ehime and Shizuoka prefecture
The Scientific World Journal 7
Okayama2Okayama3
Okayama1
1
Tokushima2
Tokushima1
Tokushima3
Ehime3Ehime2
Ehime1
Shizuoka2Shizuoka1
Shizuoka3
0
0
2
2
4
4
6
6
8 10minus8 minus6
minus6
minus4
minus4
minus2
minus2
Observations (axes F1 and F2 6827)
F2
(20
14
)
F1 (4813)
Figure 5 Scoring plots of nontargeted profiling of green algaesamples of different origin by GC-MS-SPME The profiling wascarried out based on 41 peaks and detected corresponding peak arearatios Samples were independently analyzed in triplicate The datawere analyzed by PCA using XL-STAT 20132
respectively Moreover thermal degradation products of120573-carotene including 226-trimethylcyclohexanone benzal-dehyde 266-trimethyl-2-hydroxycyclohexanone 120573-cyclo-citral 56-epoxy-120573-ionone and dihydroactinidiolide werepreviously reported [24]
After the removal of undesirable material green algae aresun dried and packaged It might be speculated that similarreactions occur during the sun drying processing of greenalgae and may have a strong impact on the quality of algaeproducts The occurrence of apocarotenoids is one of themost important indicators of authenticity for Ulva proliferaUlva linza andMonostroma nitidum
Another class of aroma compounds the aliphatic acidmethyl esters including hexadecanoic acid methyl esterand methyl linolenate was abundant in algae from Shizuokaprefecture Methyl linolenate serves as aprecursor of (EZ)-35-octadien-2-one and is one of the most odor-activecompounds [27] It has been found in cod liver oil and Ulvapertusa and contributes to the melon-like odor In this study(E Z)-35-octadien-2-onewas detected in all samples andwasmore abundant in Ulva prolifera
To explain the overall characteristics of the four algaesamples further studies are necessary to elucidate the con-tribution of single components and identify unknown com-pounds
Multi-variant analysis of known components was per-formed on the mass spectral data to explain the overallcharacteristics of the differences among the samples PCAwas performed using a transformed data set consisting ofcorrelation matrix of 41 variables yielding in 11 eigenvectorsFive factors explained 9239 of the total variance indicatingthat a reduced number of volatile compounds could explainthe overall characteristics of the four different samplesFactor 1 explained 4813 of the total variance and factor 2explained 2014 of the total variance Both factors together
enable discrimination of the four algae samples fromdifferentbiological and geographical origins (Figure 5) It is interestingthat there are fewer differences in the volatile profiles ofsamples from close geographic origins such as Tokushimaand Okayama compared with samples which are furtheraway from each other for example Tokushima and EhimeFuture studies should be performed with a higher number ofreplicates and taking into account testing sets
4 Conclusions
The volatile profiles of different commercial Japanese greenalgae samples originating from Okayama TokushimaEhime and Shizuoka were described for the first timeMultivariate analysis enabled discrimination of the samplesbased on their botanical and geographical origin Hithertothe authenticity of these commercial products is based onpackage information and this study could form the analyticalbasis of authenticity studies of dried green algae samplesusing the SPME-GC-MS-method followed by multivarianteanalysis
Conflict of Interests
The authors declare that there is no conflict of interests in thepaper
Acknowledgments
The authors are grateful for the gift of Monostroma nitidumfrom Kanetsu Sugiura Company Hamamatsu ShizuokaThey acknowledge the valuable discussion about the sensoryevaluation with Dr Bernhard Bruckner and thank all pan-elists for their support
References
[1] H Sugisawa K Nakamura and H Tamura ldquoThe aroma profileof the volatiles in marine green algae (Ulva pertusa)rdquo FoodReviews International vol 6 no 4 pp 573ndash589 1990
[2] S N Boopathy and K Kathiresan ldquoAnticancer drugs frommarine flora an overviewrdquo Journal of Oncology vol 2010Article ID 214186 18 pages 2010
[3] Food amp Agriculture Organization of the United Nations httpwwwfaoorgfoodfood-safety-qualityscientific-advicejecfajecfa-flaven
[4] T Kajiwara K Kodama A Hatanaka and K Matsui ldquoVolatilecompounds from Japanese marine brown algaerdquo in BioactiveVolatile Compounds from Plants vol 525 of ACS SymposiumSeries pp 103ndash120 1993
[5] Food Marketing amp Research Information Center httpwwwfmricorjptracenoriindexhtm
[6] P Poinot J Grua-Priol G Arvisenet et al ldquoOptimisation ofHS-SPME to study representativeness of partially baked breadodorant extractsrdquo Food Research International vol 40 no 9 pp1170ndash1184 2007
[7] D M A M Luykx and S M van Ruth ldquoAn overview of ana-lytical methods for determining the geographical origin of foodproductsrdquo Food Chemistry vol 107 no 2 pp 897ndash911 2008
8 The Scientific World Journal
[8] R Liu K Xiong Y Chao-Luo X Ze-Dai Z Min-Liu and WTong-Xue ldquoChanges in volatile compounds of a native Chinesechilli pepper (Capsicum frutescens var) during ripeningrdquo Inter-national Journal of Food Science amp Technology vol 44 no 12pp 2470ndash2475 2009
[9] I Silva S M Rocha and M A Coimbra ldquoHeadspace solidphase microextraction and gas chromatography-quadrupolemass spectrometry methodology for analysis of volatile com-pounds ofmarine salt as potential origin biomarkersrdquoAnalyticaChimica Acta vol 635 no 2 pp 167ndash174 2009
[10] K Tananuwong and S Lertsiri ldquoChanges in volatile aroma com-pounds of organic fragrant rice during storage under differentconditionsrdquo Journal of the Science of Food and Agriculture vol90 no 10 pp 1590ndash1596 2010
[11] K Kaseleht E Leitner and T Paalme ldquoDetermining aroma-active compounds in Kama flour using SPME-GCMS and GC-olfactometryrdquo Flavour and Fragrance Journal vol 26 no 2 pp122ndash128 2011
[12] A Prades R Assa M Dornier J P Pain and R BoulangerldquoCharacterisation of the volatile profile of coconut water fromfive varieties using an optimized HS-SPME-GC analysisrdquo Jour-nal of the Science of Food and Agriculture vol 92 pp 2471ndash24782012
[13] Flavornet httpwwwflavornetorg[14] S-P Hu and B S Pan ldquoModification of fish oil aroma using a
macroalgal lipoxygenaserdquo Journal of the American Oil ChemistsrsquoSociety vol 77 no 4 pp 343ndash348 2000
[15] Z Kamenarska A Ivanova R Stancheva et al ldquoVolatile com-pounds from some Black Sea red algae and their chemotaxo-nomic applicationrdquo Botanica Marina vol 49 no 1 pp 47ndash562006
[16] M E Hattab G Culioli L Piovetti S E Chitour and R VallsldquoComparison of various extraction methods for identificationand determination of volatile metabolites from the brown algaDictyopteris membranaceardquo Journal of Chromatography A vol1143 no 1-2 pp 1ndash7 2007
[17] V Gressler P Colepicolo and E Pinto ldquoUseful strategies foralgal volatile analysisrdquo Current Analytical Chemistry vol 5 no3 pp 271ndash292 2009
[18] R P Yu L P Wang S F Wu J S Che and Y M Liu ldquoAna-lysis of volatile compounds in Algal bloom water by gaschromatography-mass spectrometry and sniffingrdquo ChineseJournal of Analytical Chemistry vol 38 pp 1349ndash1352 2010
[19] A Rzama B Arreguy-San-Miguel and M Ettalibi ldquoLipidsmetabolites and essential oil from the green alga Chara vulgar-isrdquo Revue Marocaine des Sciences Agronomiques et Veterinairesvol 22 no 2 pp 65ndash70 2002
[20] M Okano and T Aratani ldquoConstituents in marine algae-Iseasonal variation of sterol hydrocarbon fatty acid and phytolfractions in Ulva pertusardquo Bulletin of the Japanese Society ofScientific Fisheries vol 45 pp 389ndash393 1979 (Japanese)
[21] Y H Hui Handbook of Fruit and Vegetable Flavors John Wileyamp Sons Hoboken NJ USA 2010
[22] P Fink E Von Elert and F Juttner ldquoVolatile foraging kair-omones in the littoral zone attraction of an herbivorous fresh-water gastropod to algal odorsrdquo Journal of Chemical Ecology vol32 no 9 pp 1867ndash1881 2006
[23] I Flament and G Ohloff ldquoVolatile constituents of algaeodoriferous constituents of seaweeds and structure of nor-terpenoids identified in Asakusa-Nori flavorrdquo in Proceedings ofthe 4th Weurman Flavour Research Symposium J Adda EdProgress in Flavor Research pp 281ndash300 Elsevier 1985
[24] M Kawakami ldquoIonone series compounds from beta-caroteneby thermal degradation in aqueous mediumrdquo Nippon Nogeika-gaku Kaishi vol 56 no 10 pp 917ndash921 1982 (Japanese)
[25] S Baldermann A N Mulyadi Z Yang et al ldquoApplication ofcentrifugal precipitation chromatography and high-speedcounter-current chromatography equipped with a spiral tubingsupport rotor for the isolation and partial characterization ofcarotenoid cleavage-like enzymes in Enteromorpha compressa(L) Neesrdquo Journal of Separation Science vol 34 no 19 pp2759ndash2764 2011
[26] R G Buttery R Teranishi L C Ling and J G TurnbaughldquoQuantitative and sensory studies on tomato paste volatilesrdquoJournal of Agricultural and Food Chemistry vol 38 no 1 pp336ndash340 1990
[27] F Ullrich and W Grosch ldquoIdentification of the most intenseodor compounds formed during autoxidation of methyl linole-nate at room temperaturerdquo Journal of the AmericanOil ChemistsSociety vol 65 no 8 pp 1313ndash1317 1988
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
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Journal of
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Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
4 The Scientific World JournalTa
ble1Vo
latilec
ompo
unds
ofdifferent
greenalgaes
amples
presentedas
relativer
atiosc
omparedto
theinternalstand
ardethyldecanoate
No
Volatilec
ompo
unds
Form
ula
Class
Orig
inOdo
rdescrip
tion
RIRe
lativec
ontents(averaged
GCpeak
area
ratio
(119899=3))
Okayama
STD
Toku
shim
aST
DEh
ime
STD
Shizuo
kaST
D1
Dod
ecane
C 10H
22Alkane
Alkane(B)
1185
ND
ND
ND
1200010
2Tridecane
C 13H
28Alkane
Fatty
acids
Alkane(B)
1297
06
000
0306
000
08ND
232
00298
3226-
Trim
ethylcyclohexano
neC 9
H16O
Ketone
Caroteno
ids
Camph
oraceous
tobaccono
tes
thujon
e-lik
e(A)
1308
07
00011
07
00026
ND
ND
4Tetradecane
C 14H
30Alkane
Fatty
acids
Alkane(B)
1397
39
00020
114
000
9771
00158
60
000
655
Tetradecene
C 14H
28Alkene
1444
05
00013
09
000
0521
00025
ND
6Pentadecane
C 15H
32Alkene
Alkane(B)
1502
836
00622
2511
01181
4205
06057
ND
7(EE)-35-Octadien-2-on
eC 8
H12O
Ketone
Fatty
acids
caroteno
ids
Alm
ond(C
)1517
ND
ND
ND
ND
8Be
nzaldehyde
C 7H
5OAldehyde
Aminoacids
Sweetstr
ong
almon
d(A
)almon
dbu
rnt
sugar(B)
1517
1700028
23
000
6809
00015
37773
74504
9Pentadeceneisomer
1C 1
5H30
Alkene
1523
24
00028
36
00025
47
00057
117
00326
10Pentadeceneisomer
2C 1
5H30
Alkene
1546
07
00011
23
00025
1000010
05
00028
11Dim
ethylsulfoxide
C 2H
6OS
Sulfu
rcompo
und
Aminoacids
1557
82
00457
165
00944
80
00500
123
00221
12(EZ)-35-Octadien-2-on
eC 8
H12O
Ketone
Fatty
acids
caroteno
ids
Melo
n-lik
e(C)
1567
27
00100
21
000
6506
00052
03
00029
13Pentadeceneisomer
3C 1
5H30
Alkene
1576
ND
ND
ND
51
00085
14266-Trim
ethyl-2
-hydroxycyclohexano
neC 9
H16O
2Ke
tone
Caroteno
ids
Sweet
tobacco-lik
earom
awith
herbaceous
underton
es(A
)
1594
86
00237
9600223
41
00053
ND
15Hexadecane
C 16H
34Alkane
Alkane(B)
1601
43
00089
56
00122
7700144
282
00563
16120573-C
yclocitral
C 10H
16O
Aldehyde
Caroteno
ids
Fresh(B)
1612
35
00085
35
00074
1400010
ND
17Hexadeceneisomer
1C 1
6H32
Alkene
1619
1200010
25
00027
21
00025
ND
18Hexadeceneisomer
2C 1
6H32
Alkene
1624
09
00024
1100026
22
000
04ND
19Safranal
C 10H
14O
Aldehyde
Caroteno
ids
1637
ND
ND
ND
ND
20Heptadecane
C 17H
36Alkane
Alkane(B)
1707
561
00610
252
00936
255
02227
124
00993
217-Heptadecene
C 17H
34Alkene
1722
29097
10740
40033
33306
39543
55587
1555
03312
22Heptadecene
isomer
1C 1
7H34
Alkene
1733
1800193
ND
120
00030
7000169
23Heptadecadieneisomer
1C 1
7H32
Alkene
1757
1034
006
041392
01109
1487
01725
643
01246
24Heptadecadieneisomer
2C 1
7H32
Alkene
1766
1000021
1200018
05
000
4707
00015
25Heptadecadieneisomer
3C 1
7H32
Alkene
1769
43
00022
22
00011
08
00074
07
00104
26Heptadecadieneisomer
4C 1
7H32
Alkene
1772
38
00037
53
00036
59
000
4111
00198
27Heptadecadieneisomer
5C 1
7H32
Alkene
1779
08
00022
ND
03
00059
05
000
9128
Octadecane
C 18H
38Alkane
Alkane(B)
1801
30
00051
16000
4232
00189
21
00059
29Octadecene
C 18H
36Alkene
1817
112
00072
128
00059
181
00085
09
00081
30120572-Io
none
C 13H
20O
Ketone
Caroteno
ids
Warmw
oody
violet-floral(A
)1842
46
00039
56
00139
1800085
ND
The Scientific World Journal 5
Table1Con
tinued
No
Volatilec
ompo
unds
Form
ula
Class
Orig
inOdo
rdescrip
tion
RIRe
lativec
ontents(averaged
GCpeak
area
ratio
(119899=3))
Okayama
STD
Toku
shim
aST
DEh
ime
STD
Shizuo
kaST
D31
Non
adecane
C 19H
40Alkane
Alkane(B)
1898
29
00119
1100039
20
00029
07
00033
32120573-Io
none
C 13H
20O
Ketone
Caroteno
ids
Warmw
oody
dry(A
)1927
125
01087
157
00144
59
000
4007
00031
33Maltol
C 6H
6O3
Ketone
Caramel-
butte
rscotch(A
)caramel(B)
1960
06
00082
ND
ND
1000059
34120573-Io
none
epoxide
C 13H
20O
2Ke
tone
Caroteno
ids
Sweetb
erry
(A)
1980
21
00181
28
00025
09
000
06ND
35Methyltetradecano
ate
C 15H
30O
2Ester
Fainto
nion
ho
ney(A
)orris
(A)(B)
2010
09
00051
00
000
0013
00017
1700036
36Pentadecanal
C 15H
30O
Aldehyde
Fresh(B)
2034
1800103
31
00033
1800103
ND
3761014
-Trim
ethyl-2
-pentadecanon
eC 1
8H36O
Ketone
Caroteno
ids
2139
29
00168
67
00174
7000160
74004
27
38Hexadecanoica
cid
methyleste
rC 1
7H34O
2Ester
Fatty
acids
2217
52
00210
22
00038
9000133
22
00029
39Dihydroactin
idiolid
eC 1
1H16O
2Ke
tone
Caroteno
ids
Musky
orcoum
arin-like
(A)
2347
30
00363
84
00199
42
00022
04
00034
40Methyllinolenate
C 19H
32O
2Ester
Fatty
acids
2566
41
00390
27
000
6373
00268
34
00057
41Ph
ytol
C 20H
40O
Alcoh
olCh
loroph
yll
Faintfl
oral(A
)flo
wer
(B)
2580
28
00191
1200050
09
00023
07
00071
(A)F
oodandAgriculture
Organizationof
theu
nitednatio
ns(http
wwwfaoorg)(B)
Flavornet(httpwwwflavornetorg)and(C
)HuandPan
2000
[14]
6 The Scientific World Journal
DodecaneTridecane
Trimethylcyclohexanone
Tetradecane
TetradecenePentadecane
Benzaldehyde
Pentadecene
Pentadecene
Dimethyl sulfoxide
Pentadecene
hydroxycyclohexanone
Hexadecane
Hexadecene
Hexadecene
Safranal
Heptadecane
Heptadecene
Heptadecene
Heptadecadiene
HeptadecadieneHeptadecadiene
Heptadecadiene
Heptadecadiene
Octadecane
Octadecene
Nonadecane
Maltol
Methyl tetradecanoate
Pentadecanal
pentylidenefuran-2-one
Hexadecanoic acid methylester
Dihydroactinidiolide
Methyl linolenate
Phytol
0
025
05
075
1
025 050 075 1
minus025
minus025
minus075
minus075
minus1
minus1
minus05
minus05
120573-ionone epoxide120573-Ionone
266-Trimethyl-2-
120572-Ionone120573-Cyclocitral
35-Octadien-2-one
61014-Dimethyl
35-Octadiene-2-one
F1 (4813)
226-
Variables (axes F1 and F2 6827)F2
(20
14
)
Figure 4 Correlation circle of volatile compounds from different green algae samples The profiling was carried out based on 41 peaks anddetected corresponding peak area ratios Samples were independently analyzed in triplicate The data was analyzed by PCA using XL-STAT20132
Our analysis revealed benzaldehyde an important com-pound in algae from Shizuoka prefecture originated from theamino acid biosynthesis pathway Benzaldehyde contributesto the sweet almond odor of fruits and flowers and is char-acterized by low odor thresholds (350ndash3500 ppb) Benzalde-hyde can also be liberated from glycosidically bound precur-sors in various foods In addition it has been reported thatconcentrations increase during manufacturing processes forexample production of apple puree or roasting of sesameseeds [21]
Several hydrocarbons such as tridecane pentadecanehexadecane and dodecane were identified as relevant odorcompounds in seaweed from Shizuoka prefecture
It is noticeable that the proportion of volatile apoc-arotenoids is remarkably high in the investigated algaevarieties The importance of carotenoid-derived flavor com-pounds in algae has been previously reported Volatile apoc-arotenoids such as the potent flavor compound120573-ionone areproduced by a diversity of algae taxa for example Ulothrixfimbriata and Asakusa Nori (Porphyra tenera) [22 23] Apartfrom chemical formation pathways [24] it has been demon-strated that functional carotenoid-cleavage like enzymes
contribute to the formation of volatile apocarotenoids in algae[25]
226-Trimethylcyclohexanone (E Z)-35-octadiene-2-one 266-trimethyl-2-hydroxycyclohexa-none 120572-ionone 120573-ionone and 120573-ionone epoxide are abundant in Okayamaand Tokushima Dihydroactinidiolide makes an importantcontribution to the volatile profile of algae from TokushimaIt is also an important component in green tea with a sweetpeach-like flavor [24] In addition 120573-cyclocitral and phytolare characteristic compounds influencing the flavor of algaefrom Okayama and Tokushima prefecture they contributeto fresh and floral odors respectively [18] The ketonessuch as 120573-cyclocitral 120573-ionone and 120573-ionone epoxide andphytol are generated via degradation of carotenoids 120572-Ionone contributes to the violet wood odor 120573-ionone con-tributes to the violet-like and characteristic seaweed odor 120573-ionone epoxide contributes to the sweet berry odor Theseare important aroma impact compounds characterized byvery low odor thresholds for example 120573-ionone has an odorthreshold of 0007 ppm [26] 120573-Ionone accounts for 125157 59 and 07 of the volatiles in the algae harvestedfromOkayama Tokushima Ehime and Shizuoka prefecture
The Scientific World Journal 7
Okayama2Okayama3
Okayama1
1
Tokushima2
Tokushima1
Tokushima3
Ehime3Ehime2
Ehime1
Shizuoka2Shizuoka1
Shizuoka3
0
0
2
2
4
4
6
6
8 10minus8 minus6
minus6
minus4
minus4
minus2
minus2
Observations (axes F1 and F2 6827)
F2
(20
14
)
F1 (4813)
Figure 5 Scoring plots of nontargeted profiling of green algaesamples of different origin by GC-MS-SPME The profiling wascarried out based on 41 peaks and detected corresponding peak arearatios Samples were independently analyzed in triplicate The datawere analyzed by PCA using XL-STAT 20132
respectively Moreover thermal degradation products of120573-carotene including 226-trimethylcyclohexanone benzal-dehyde 266-trimethyl-2-hydroxycyclohexanone 120573-cyclo-citral 56-epoxy-120573-ionone and dihydroactinidiolide werepreviously reported [24]
After the removal of undesirable material green algae aresun dried and packaged It might be speculated that similarreactions occur during the sun drying processing of greenalgae and may have a strong impact on the quality of algaeproducts The occurrence of apocarotenoids is one of themost important indicators of authenticity for Ulva proliferaUlva linza andMonostroma nitidum
Another class of aroma compounds the aliphatic acidmethyl esters including hexadecanoic acid methyl esterand methyl linolenate was abundant in algae from Shizuokaprefecture Methyl linolenate serves as aprecursor of (EZ)-35-octadien-2-one and is one of the most odor-activecompounds [27] It has been found in cod liver oil and Ulvapertusa and contributes to the melon-like odor In this study(E Z)-35-octadien-2-onewas detected in all samples andwasmore abundant in Ulva prolifera
To explain the overall characteristics of the four algaesamples further studies are necessary to elucidate the con-tribution of single components and identify unknown com-pounds
Multi-variant analysis of known components was per-formed on the mass spectral data to explain the overallcharacteristics of the differences among the samples PCAwas performed using a transformed data set consisting ofcorrelation matrix of 41 variables yielding in 11 eigenvectorsFive factors explained 9239 of the total variance indicatingthat a reduced number of volatile compounds could explainthe overall characteristics of the four different samplesFactor 1 explained 4813 of the total variance and factor 2explained 2014 of the total variance Both factors together
enable discrimination of the four algae samples fromdifferentbiological and geographical origins (Figure 5) It is interestingthat there are fewer differences in the volatile profiles ofsamples from close geographic origins such as Tokushimaand Okayama compared with samples which are furtheraway from each other for example Tokushima and EhimeFuture studies should be performed with a higher number ofreplicates and taking into account testing sets
4 Conclusions
The volatile profiles of different commercial Japanese greenalgae samples originating from Okayama TokushimaEhime and Shizuoka were described for the first timeMultivariate analysis enabled discrimination of the samplesbased on their botanical and geographical origin Hithertothe authenticity of these commercial products is based onpackage information and this study could form the analyticalbasis of authenticity studies of dried green algae samplesusing the SPME-GC-MS-method followed by multivarianteanalysis
Conflict of Interests
The authors declare that there is no conflict of interests in thepaper
Acknowledgments
The authors are grateful for the gift of Monostroma nitidumfrom Kanetsu Sugiura Company Hamamatsu ShizuokaThey acknowledge the valuable discussion about the sensoryevaluation with Dr Bernhard Bruckner and thank all pan-elists for their support
References
[1] H Sugisawa K Nakamura and H Tamura ldquoThe aroma profileof the volatiles in marine green algae (Ulva pertusa)rdquo FoodReviews International vol 6 no 4 pp 573ndash589 1990
[2] S N Boopathy and K Kathiresan ldquoAnticancer drugs frommarine flora an overviewrdquo Journal of Oncology vol 2010Article ID 214186 18 pages 2010
[3] Food amp Agriculture Organization of the United Nations httpwwwfaoorgfoodfood-safety-qualityscientific-advicejecfajecfa-flaven
[4] T Kajiwara K Kodama A Hatanaka and K Matsui ldquoVolatilecompounds from Japanese marine brown algaerdquo in BioactiveVolatile Compounds from Plants vol 525 of ACS SymposiumSeries pp 103ndash120 1993
[5] Food Marketing amp Research Information Center httpwwwfmricorjptracenoriindexhtm
[6] P Poinot J Grua-Priol G Arvisenet et al ldquoOptimisation ofHS-SPME to study representativeness of partially baked breadodorant extractsrdquo Food Research International vol 40 no 9 pp1170ndash1184 2007
[7] D M A M Luykx and S M van Ruth ldquoAn overview of ana-lytical methods for determining the geographical origin of foodproductsrdquo Food Chemistry vol 107 no 2 pp 897ndash911 2008
8 The Scientific World Journal
[8] R Liu K Xiong Y Chao-Luo X Ze-Dai Z Min-Liu and WTong-Xue ldquoChanges in volatile compounds of a native Chinesechilli pepper (Capsicum frutescens var) during ripeningrdquo Inter-national Journal of Food Science amp Technology vol 44 no 12pp 2470ndash2475 2009
[9] I Silva S M Rocha and M A Coimbra ldquoHeadspace solidphase microextraction and gas chromatography-quadrupolemass spectrometry methodology for analysis of volatile com-pounds ofmarine salt as potential origin biomarkersrdquoAnalyticaChimica Acta vol 635 no 2 pp 167ndash174 2009
[10] K Tananuwong and S Lertsiri ldquoChanges in volatile aroma com-pounds of organic fragrant rice during storage under differentconditionsrdquo Journal of the Science of Food and Agriculture vol90 no 10 pp 1590ndash1596 2010
[11] K Kaseleht E Leitner and T Paalme ldquoDetermining aroma-active compounds in Kama flour using SPME-GCMS and GC-olfactometryrdquo Flavour and Fragrance Journal vol 26 no 2 pp122ndash128 2011
[12] A Prades R Assa M Dornier J P Pain and R BoulangerldquoCharacterisation of the volatile profile of coconut water fromfive varieties using an optimized HS-SPME-GC analysisrdquo Jour-nal of the Science of Food and Agriculture vol 92 pp 2471ndash24782012
[13] Flavornet httpwwwflavornetorg[14] S-P Hu and B S Pan ldquoModification of fish oil aroma using a
macroalgal lipoxygenaserdquo Journal of the American Oil ChemistsrsquoSociety vol 77 no 4 pp 343ndash348 2000
[15] Z Kamenarska A Ivanova R Stancheva et al ldquoVolatile com-pounds from some Black Sea red algae and their chemotaxo-nomic applicationrdquo Botanica Marina vol 49 no 1 pp 47ndash562006
[16] M E Hattab G Culioli L Piovetti S E Chitour and R VallsldquoComparison of various extraction methods for identificationand determination of volatile metabolites from the brown algaDictyopteris membranaceardquo Journal of Chromatography A vol1143 no 1-2 pp 1ndash7 2007
[17] V Gressler P Colepicolo and E Pinto ldquoUseful strategies foralgal volatile analysisrdquo Current Analytical Chemistry vol 5 no3 pp 271ndash292 2009
[18] R P Yu L P Wang S F Wu J S Che and Y M Liu ldquoAna-lysis of volatile compounds in Algal bloom water by gaschromatography-mass spectrometry and sniffingrdquo ChineseJournal of Analytical Chemistry vol 38 pp 1349ndash1352 2010
[19] A Rzama B Arreguy-San-Miguel and M Ettalibi ldquoLipidsmetabolites and essential oil from the green alga Chara vulgar-isrdquo Revue Marocaine des Sciences Agronomiques et Veterinairesvol 22 no 2 pp 65ndash70 2002
[20] M Okano and T Aratani ldquoConstituents in marine algae-Iseasonal variation of sterol hydrocarbon fatty acid and phytolfractions in Ulva pertusardquo Bulletin of the Japanese Society ofScientific Fisheries vol 45 pp 389ndash393 1979 (Japanese)
[21] Y H Hui Handbook of Fruit and Vegetable Flavors John Wileyamp Sons Hoboken NJ USA 2010
[22] P Fink E Von Elert and F Juttner ldquoVolatile foraging kair-omones in the littoral zone attraction of an herbivorous fresh-water gastropod to algal odorsrdquo Journal of Chemical Ecology vol32 no 9 pp 1867ndash1881 2006
[23] I Flament and G Ohloff ldquoVolatile constituents of algaeodoriferous constituents of seaweeds and structure of nor-terpenoids identified in Asakusa-Nori flavorrdquo in Proceedings ofthe 4th Weurman Flavour Research Symposium J Adda EdProgress in Flavor Research pp 281ndash300 Elsevier 1985
[24] M Kawakami ldquoIonone series compounds from beta-caroteneby thermal degradation in aqueous mediumrdquo Nippon Nogeika-gaku Kaishi vol 56 no 10 pp 917ndash921 1982 (Japanese)
[25] S Baldermann A N Mulyadi Z Yang et al ldquoApplication ofcentrifugal precipitation chromatography and high-speedcounter-current chromatography equipped with a spiral tubingsupport rotor for the isolation and partial characterization ofcarotenoid cleavage-like enzymes in Enteromorpha compressa(L) Neesrdquo Journal of Separation Science vol 34 no 19 pp2759ndash2764 2011
[26] R G Buttery R Teranishi L C Ling and J G TurnbaughldquoQuantitative and sensory studies on tomato paste volatilesrdquoJournal of Agricultural and Food Chemistry vol 38 no 1 pp336ndash340 1990
[27] F Ullrich and W Grosch ldquoIdentification of the most intenseodor compounds formed during autoxidation of methyl linole-nate at room temperaturerdquo Journal of the AmericanOil ChemistsSociety vol 65 no 8 pp 1313ndash1317 1988
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
The Scientific World Journal 5
Table1Con
tinued
No
Volatilec
ompo
unds
Form
ula
Class
Orig
inOdo
rdescrip
tion
RIRe
lativec
ontents(averaged
GCpeak
area
ratio
(119899=3))
Okayama
STD
Toku
shim
aST
DEh
ime
STD
Shizuo
kaST
D31
Non
adecane
C 19H
40Alkane
Alkane(B)
1898
29
00119
1100039
20
00029
07
00033
32120573-Io
none
C 13H
20O
Ketone
Caroteno
ids
Warmw
oody
dry(A
)1927
125
01087
157
00144
59
000
4007
00031
33Maltol
C 6H
6O3
Ketone
Caramel-
butte
rscotch(A
)caramel(B)
1960
06
00082
ND
ND
1000059
34120573-Io
none
epoxide
C 13H
20O
2Ke
tone
Caroteno
ids
Sweetb
erry
(A)
1980
21
00181
28
00025
09
000
06ND
35Methyltetradecano
ate
C 15H
30O
2Ester
Fainto
nion
ho
ney(A
)orris
(A)(B)
2010
09
00051
00
000
0013
00017
1700036
36Pentadecanal
C 15H
30O
Aldehyde
Fresh(B)
2034
1800103
31
00033
1800103
ND
3761014
-Trim
ethyl-2
-pentadecanon
eC 1
8H36O
Ketone
Caroteno
ids
2139
29
00168
67
00174
7000160
74004
27
38Hexadecanoica
cid
methyleste
rC 1
7H34O
2Ester
Fatty
acids
2217
52
00210
22
00038
9000133
22
00029
39Dihydroactin
idiolid
eC 1
1H16O
2Ke
tone
Caroteno
ids
Musky
orcoum
arin-like
(A)
2347
30
00363
84
00199
42
00022
04
00034
40Methyllinolenate
C 19H
32O
2Ester
Fatty
acids
2566
41
00390
27
000
6373
00268
34
00057
41Ph
ytol
C 20H
40O
Alcoh
olCh
loroph
yll
Faintfl
oral(A
)flo
wer
(B)
2580
28
00191
1200050
09
00023
07
00071
(A)F
oodandAgriculture
Organizationof
theu
nitednatio
ns(http
wwwfaoorg)(B)
Flavornet(httpwwwflavornetorg)and(C
)HuandPan
2000
[14]
6 The Scientific World Journal
DodecaneTridecane
Trimethylcyclohexanone
Tetradecane
TetradecenePentadecane
Benzaldehyde
Pentadecene
Pentadecene
Dimethyl sulfoxide
Pentadecene
hydroxycyclohexanone
Hexadecane
Hexadecene
Hexadecene
Safranal
Heptadecane
Heptadecene
Heptadecene
Heptadecadiene
HeptadecadieneHeptadecadiene
Heptadecadiene
Heptadecadiene
Octadecane
Octadecene
Nonadecane
Maltol
Methyl tetradecanoate
Pentadecanal
pentylidenefuran-2-one
Hexadecanoic acid methylester
Dihydroactinidiolide
Methyl linolenate
Phytol
0
025
05
075
1
025 050 075 1
minus025
minus025
minus075
minus075
minus1
minus1
minus05
minus05
120573-ionone epoxide120573-Ionone
266-Trimethyl-2-
120572-Ionone120573-Cyclocitral
35-Octadien-2-one
61014-Dimethyl
35-Octadiene-2-one
F1 (4813)
226-
Variables (axes F1 and F2 6827)F2
(20
14
)
Figure 4 Correlation circle of volatile compounds from different green algae samples The profiling was carried out based on 41 peaks anddetected corresponding peak area ratios Samples were independently analyzed in triplicate The data was analyzed by PCA using XL-STAT20132
Our analysis revealed benzaldehyde an important com-pound in algae from Shizuoka prefecture originated from theamino acid biosynthesis pathway Benzaldehyde contributesto the sweet almond odor of fruits and flowers and is char-acterized by low odor thresholds (350ndash3500 ppb) Benzalde-hyde can also be liberated from glycosidically bound precur-sors in various foods In addition it has been reported thatconcentrations increase during manufacturing processes forexample production of apple puree or roasting of sesameseeds [21]
Several hydrocarbons such as tridecane pentadecanehexadecane and dodecane were identified as relevant odorcompounds in seaweed from Shizuoka prefecture
It is noticeable that the proportion of volatile apoc-arotenoids is remarkably high in the investigated algaevarieties The importance of carotenoid-derived flavor com-pounds in algae has been previously reported Volatile apoc-arotenoids such as the potent flavor compound120573-ionone areproduced by a diversity of algae taxa for example Ulothrixfimbriata and Asakusa Nori (Porphyra tenera) [22 23] Apartfrom chemical formation pathways [24] it has been demon-strated that functional carotenoid-cleavage like enzymes
contribute to the formation of volatile apocarotenoids in algae[25]
226-Trimethylcyclohexanone (E Z)-35-octadiene-2-one 266-trimethyl-2-hydroxycyclohexa-none 120572-ionone 120573-ionone and 120573-ionone epoxide are abundant in Okayamaand Tokushima Dihydroactinidiolide makes an importantcontribution to the volatile profile of algae from TokushimaIt is also an important component in green tea with a sweetpeach-like flavor [24] In addition 120573-cyclocitral and phytolare characteristic compounds influencing the flavor of algaefrom Okayama and Tokushima prefecture they contributeto fresh and floral odors respectively [18] The ketonessuch as 120573-cyclocitral 120573-ionone and 120573-ionone epoxide andphytol are generated via degradation of carotenoids 120572-Ionone contributes to the violet wood odor 120573-ionone con-tributes to the violet-like and characteristic seaweed odor 120573-ionone epoxide contributes to the sweet berry odor Theseare important aroma impact compounds characterized byvery low odor thresholds for example 120573-ionone has an odorthreshold of 0007 ppm [26] 120573-Ionone accounts for 125157 59 and 07 of the volatiles in the algae harvestedfromOkayama Tokushima Ehime and Shizuoka prefecture
The Scientific World Journal 7
Okayama2Okayama3
Okayama1
1
Tokushima2
Tokushima1
Tokushima3
Ehime3Ehime2
Ehime1
Shizuoka2Shizuoka1
Shizuoka3
0
0
2
2
4
4
6
6
8 10minus8 minus6
minus6
minus4
minus4
minus2
minus2
Observations (axes F1 and F2 6827)
F2
(20
14
)
F1 (4813)
Figure 5 Scoring plots of nontargeted profiling of green algaesamples of different origin by GC-MS-SPME The profiling wascarried out based on 41 peaks and detected corresponding peak arearatios Samples were independently analyzed in triplicate The datawere analyzed by PCA using XL-STAT 20132
respectively Moreover thermal degradation products of120573-carotene including 226-trimethylcyclohexanone benzal-dehyde 266-trimethyl-2-hydroxycyclohexanone 120573-cyclo-citral 56-epoxy-120573-ionone and dihydroactinidiolide werepreviously reported [24]
After the removal of undesirable material green algae aresun dried and packaged It might be speculated that similarreactions occur during the sun drying processing of greenalgae and may have a strong impact on the quality of algaeproducts The occurrence of apocarotenoids is one of themost important indicators of authenticity for Ulva proliferaUlva linza andMonostroma nitidum
Another class of aroma compounds the aliphatic acidmethyl esters including hexadecanoic acid methyl esterand methyl linolenate was abundant in algae from Shizuokaprefecture Methyl linolenate serves as aprecursor of (EZ)-35-octadien-2-one and is one of the most odor-activecompounds [27] It has been found in cod liver oil and Ulvapertusa and contributes to the melon-like odor In this study(E Z)-35-octadien-2-onewas detected in all samples andwasmore abundant in Ulva prolifera
To explain the overall characteristics of the four algaesamples further studies are necessary to elucidate the con-tribution of single components and identify unknown com-pounds
Multi-variant analysis of known components was per-formed on the mass spectral data to explain the overallcharacteristics of the differences among the samples PCAwas performed using a transformed data set consisting ofcorrelation matrix of 41 variables yielding in 11 eigenvectorsFive factors explained 9239 of the total variance indicatingthat a reduced number of volatile compounds could explainthe overall characteristics of the four different samplesFactor 1 explained 4813 of the total variance and factor 2explained 2014 of the total variance Both factors together
enable discrimination of the four algae samples fromdifferentbiological and geographical origins (Figure 5) It is interestingthat there are fewer differences in the volatile profiles ofsamples from close geographic origins such as Tokushimaand Okayama compared with samples which are furtheraway from each other for example Tokushima and EhimeFuture studies should be performed with a higher number ofreplicates and taking into account testing sets
4 Conclusions
The volatile profiles of different commercial Japanese greenalgae samples originating from Okayama TokushimaEhime and Shizuoka were described for the first timeMultivariate analysis enabled discrimination of the samplesbased on their botanical and geographical origin Hithertothe authenticity of these commercial products is based onpackage information and this study could form the analyticalbasis of authenticity studies of dried green algae samplesusing the SPME-GC-MS-method followed by multivarianteanalysis
Conflict of Interests
The authors declare that there is no conflict of interests in thepaper
Acknowledgments
The authors are grateful for the gift of Monostroma nitidumfrom Kanetsu Sugiura Company Hamamatsu ShizuokaThey acknowledge the valuable discussion about the sensoryevaluation with Dr Bernhard Bruckner and thank all pan-elists for their support
References
[1] H Sugisawa K Nakamura and H Tamura ldquoThe aroma profileof the volatiles in marine green algae (Ulva pertusa)rdquo FoodReviews International vol 6 no 4 pp 573ndash589 1990
[2] S N Boopathy and K Kathiresan ldquoAnticancer drugs frommarine flora an overviewrdquo Journal of Oncology vol 2010Article ID 214186 18 pages 2010
[3] Food amp Agriculture Organization of the United Nations httpwwwfaoorgfoodfood-safety-qualityscientific-advicejecfajecfa-flaven
[4] T Kajiwara K Kodama A Hatanaka and K Matsui ldquoVolatilecompounds from Japanese marine brown algaerdquo in BioactiveVolatile Compounds from Plants vol 525 of ACS SymposiumSeries pp 103ndash120 1993
[5] Food Marketing amp Research Information Center httpwwwfmricorjptracenoriindexhtm
[6] P Poinot J Grua-Priol G Arvisenet et al ldquoOptimisation ofHS-SPME to study representativeness of partially baked breadodorant extractsrdquo Food Research International vol 40 no 9 pp1170ndash1184 2007
[7] D M A M Luykx and S M van Ruth ldquoAn overview of ana-lytical methods for determining the geographical origin of foodproductsrdquo Food Chemistry vol 107 no 2 pp 897ndash911 2008
8 The Scientific World Journal
[8] R Liu K Xiong Y Chao-Luo X Ze-Dai Z Min-Liu and WTong-Xue ldquoChanges in volatile compounds of a native Chinesechilli pepper (Capsicum frutescens var) during ripeningrdquo Inter-national Journal of Food Science amp Technology vol 44 no 12pp 2470ndash2475 2009
[9] I Silva S M Rocha and M A Coimbra ldquoHeadspace solidphase microextraction and gas chromatography-quadrupolemass spectrometry methodology for analysis of volatile com-pounds ofmarine salt as potential origin biomarkersrdquoAnalyticaChimica Acta vol 635 no 2 pp 167ndash174 2009
[10] K Tananuwong and S Lertsiri ldquoChanges in volatile aroma com-pounds of organic fragrant rice during storage under differentconditionsrdquo Journal of the Science of Food and Agriculture vol90 no 10 pp 1590ndash1596 2010
[11] K Kaseleht E Leitner and T Paalme ldquoDetermining aroma-active compounds in Kama flour using SPME-GCMS and GC-olfactometryrdquo Flavour and Fragrance Journal vol 26 no 2 pp122ndash128 2011
[12] A Prades R Assa M Dornier J P Pain and R BoulangerldquoCharacterisation of the volatile profile of coconut water fromfive varieties using an optimized HS-SPME-GC analysisrdquo Jour-nal of the Science of Food and Agriculture vol 92 pp 2471ndash24782012
[13] Flavornet httpwwwflavornetorg[14] S-P Hu and B S Pan ldquoModification of fish oil aroma using a
macroalgal lipoxygenaserdquo Journal of the American Oil ChemistsrsquoSociety vol 77 no 4 pp 343ndash348 2000
[15] Z Kamenarska A Ivanova R Stancheva et al ldquoVolatile com-pounds from some Black Sea red algae and their chemotaxo-nomic applicationrdquo Botanica Marina vol 49 no 1 pp 47ndash562006
[16] M E Hattab G Culioli L Piovetti S E Chitour and R VallsldquoComparison of various extraction methods for identificationand determination of volatile metabolites from the brown algaDictyopteris membranaceardquo Journal of Chromatography A vol1143 no 1-2 pp 1ndash7 2007
[17] V Gressler P Colepicolo and E Pinto ldquoUseful strategies foralgal volatile analysisrdquo Current Analytical Chemistry vol 5 no3 pp 271ndash292 2009
[18] R P Yu L P Wang S F Wu J S Che and Y M Liu ldquoAna-lysis of volatile compounds in Algal bloom water by gaschromatography-mass spectrometry and sniffingrdquo ChineseJournal of Analytical Chemistry vol 38 pp 1349ndash1352 2010
[19] A Rzama B Arreguy-San-Miguel and M Ettalibi ldquoLipidsmetabolites and essential oil from the green alga Chara vulgar-isrdquo Revue Marocaine des Sciences Agronomiques et Veterinairesvol 22 no 2 pp 65ndash70 2002
[20] M Okano and T Aratani ldquoConstituents in marine algae-Iseasonal variation of sterol hydrocarbon fatty acid and phytolfractions in Ulva pertusardquo Bulletin of the Japanese Society ofScientific Fisheries vol 45 pp 389ndash393 1979 (Japanese)
[21] Y H Hui Handbook of Fruit and Vegetable Flavors John Wileyamp Sons Hoboken NJ USA 2010
[22] P Fink E Von Elert and F Juttner ldquoVolatile foraging kair-omones in the littoral zone attraction of an herbivorous fresh-water gastropod to algal odorsrdquo Journal of Chemical Ecology vol32 no 9 pp 1867ndash1881 2006
[23] I Flament and G Ohloff ldquoVolatile constituents of algaeodoriferous constituents of seaweeds and structure of nor-terpenoids identified in Asakusa-Nori flavorrdquo in Proceedings ofthe 4th Weurman Flavour Research Symposium J Adda EdProgress in Flavor Research pp 281ndash300 Elsevier 1985
[24] M Kawakami ldquoIonone series compounds from beta-caroteneby thermal degradation in aqueous mediumrdquo Nippon Nogeika-gaku Kaishi vol 56 no 10 pp 917ndash921 1982 (Japanese)
[25] S Baldermann A N Mulyadi Z Yang et al ldquoApplication ofcentrifugal precipitation chromatography and high-speedcounter-current chromatography equipped with a spiral tubingsupport rotor for the isolation and partial characterization ofcarotenoid cleavage-like enzymes in Enteromorpha compressa(L) Neesrdquo Journal of Separation Science vol 34 no 19 pp2759ndash2764 2011
[26] R G Buttery R Teranishi L C Ling and J G TurnbaughldquoQuantitative and sensory studies on tomato paste volatilesrdquoJournal of Agricultural and Food Chemistry vol 38 no 1 pp336ndash340 1990
[27] F Ullrich and W Grosch ldquoIdentification of the most intenseodor compounds formed during autoxidation of methyl linole-nate at room temperaturerdquo Journal of the AmericanOil ChemistsSociety vol 65 no 8 pp 1313ndash1317 1988
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
6 The Scientific World Journal
DodecaneTridecane
Trimethylcyclohexanone
Tetradecane
TetradecenePentadecane
Benzaldehyde
Pentadecene
Pentadecene
Dimethyl sulfoxide
Pentadecene
hydroxycyclohexanone
Hexadecane
Hexadecene
Hexadecene
Safranal
Heptadecane
Heptadecene
Heptadecene
Heptadecadiene
HeptadecadieneHeptadecadiene
Heptadecadiene
Heptadecadiene
Octadecane
Octadecene
Nonadecane
Maltol
Methyl tetradecanoate
Pentadecanal
pentylidenefuran-2-one
Hexadecanoic acid methylester
Dihydroactinidiolide
Methyl linolenate
Phytol
0
025
05
075
1
025 050 075 1
minus025
minus025
minus075
minus075
minus1
minus1
minus05
minus05
120573-ionone epoxide120573-Ionone
266-Trimethyl-2-
120572-Ionone120573-Cyclocitral
35-Octadien-2-one
61014-Dimethyl
35-Octadiene-2-one
F1 (4813)
226-
Variables (axes F1 and F2 6827)F2
(20
14
)
Figure 4 Correlation circle of volatile compounds from different green algae samples The profiling was carried out based on 41 peaks anddetected corresponding peak area ratios Samples were independently analyzed in triplicate The data was analyzed by PCA using XL-STAT20132
Our analysis revealed benzaldehyde an important com-pound in algae from Shizuoka prefecture originated from theamino acid biosynthesis pathway Benzaldehyde contributesto the sweet almond odor of fruits and flowers and is char-acterized by low odor thresholds (350ndash3500 ppb) Benzalde-hyde can also be liberated from glycosidically bound precur-sors in various foods In addition it has been reported thatconcentrations increase during manufacturing processes forexample production of apple puree or roasting of sesameseeds [21]
Several hydrocarbons such as tridecane pentadecanehexadecane and dodecane were identified as relevant odorcompounds in seaweed from Shizuoka prefecture
It is noticeable that the proportion of volatile apoc-arotenoids is remarkably high in the investigated algaevarieties The importance of carotenoid-derived flavor com-pounds in algae has been previously reported Volatile apoc-arotenoids such as the potent flavor compound120573-ionone areproduced by a diversity of algae taxa for example Ulothrixfimbriata and Asakusa Nori (Porphyra tenera) [22 23] Apartfrom chemical formation pathways [24] it has been demon-strated that functional carotenoid-cleavage like enzymes
contribute to the formation of volatile apocarotenoids in algae[25]
226-Trimethylcyclohexanone (E Z)-35-octadiene-2-one 266-trimethyl-2-hydroxycyclohexa-none 120572-ionone 120573-ionone and 120573-ionone epoxide are abundant in Okayamaand Tokushima Dihydroactinidiolide makes an importantcontribution to the volatile profile of algae from TokushimaIt is also an important component in green tea with a sweetpeach-like flavor [24] In addition 120573-cyclocitral and phytolare characteristic compounds influencing the flavor of algaefrom Okayama and Tokushima prefecture they contributeto fresh and floral odors respectively [18] The ketonessuch as 120573-cyclocitral 120573-ionone and 120573-ionone epoxide andphytol are generated via degradation of carotenoids 120572-Ionone contributes to the violet wood odor 120573-ionone con-tributes to the violet-like and characteristic seaweed odor 120573-ionone epoxide contributes to the sweet berry odor Theseare important aroma impact compounds characterized byvery low odor thresholds for example 120573-ionone has an odorthreshold of 0007 ppm [26] 120573-Ionone accounts for 125157 59 and 07 of the volatiles in the algae harvestedfromOkayama Tokushima Ehime and Shizuoka prefecture
The Scientific World Journal 7
Okayama2Okayama3
Okayama1
1
Tokushima2
Tokushima1
Tokushima3
Ehime3Ehime2
Ehime1
Shizuoka2Shizuoka1
Shizuoka3
0
0
2
2
4
4
6
6
8 10minus8 minus6
minus6
minus4
minus4
minus2
minus2
Observations (axes F1 and F2 6827)
F2
(20
14
)
F1 (4813)
Figure 5 Scoring plots of nontargeted profiling of green algaesamples of different origin by GC-MS-SPME The profiling wascarried out based on 41 peaks and detected corresponding peak arearatios Samples were independently analyzed in triplicate The datawere analyzed by PCA using XL-STAT 20132
respectively Moreover thermal degradation products of120573-carotene including 226-trimethylcyclohexanone benzal-dehyde 266-trimethyl-2-hydroxycyclohexanone 120573-cyclo-citral 56-epoxy-120573-ionone and dihydroactinidiolide werepreviously reported [24]
After the removal of undesirable material green algae aresun dried and packaged It might be speculated that similarreactions occur during the sun drying processing of greenalgae and may have a strong impact on the quality of algaeproducts The occurrence of apocarotenoids is one of themost important indicators of authenticity for Ulva proliferaUlva linza andMonostroma nitidum
Another class of aroma compounds the aliphatic acidmethyl esters including hexadecanoic acid methyl esterand methyl linolenate was abundant in algae from Shizuokaprefecture Methyl linolenate serves as aprecursor of (EZ)-35-octadien-2-one and is one of the most odor-activecompounds [27] It has been found in cod liver oil and Ulvapertusa and contributes to the melon-like odor In this study(E Z)-35-octadien-2-onewas detected in all samples andwasmore abundant in Ulva prolifera
To explain the overall characteristics of the four algaesamples further studies are necessary to elucidate the con-tribution of single components and identify unknown com-pounds
Multi-variant analysis of known components was per-formed on the mass spectral data to explain the overallcharacteristics of the differences among the samples PCAwas performed using a transformed data set consisting ofcorrelation matrix of 41 variables yielding in 11 eigenvectorsFive factors explained 9239 of the total variance indicatingthat a reduced number of volatile compounds could explainthe overall characteristics of the four different samplesFactor 1 explained 4813 of the total variance and factor 2explained 2014 of the total variance Both factors together
enable discrimination of the four algae samples fromdifferentbiological and geographical origins (Figure 5) It is interestingthat there are fewer differences in the volatile profiles ofsamples from close geographic origins such as Tokushimaand Okayama compared with samples which are furtheraway from each other for example Tokushima and EhimeFuture studies should be performed with a higher number ofreplicates and taking into account testing sets
4 Conclusions
The volatile profiles of different commercial Japanese greenalgae samples originating from Okayama TokushimaEhime and Shizuoka were described for the first timeMultivariate analysis enabled discrimination of the samplesbased on their botanical and geographical origin Hithertothe authenticity of these commercial products is based onpackage information and this study could form the analyticalbasis of authenticity studies of dried green algae samplesusing the SPME-GC-MS-method followed by multivarianteanalysis
Conflict of Interests
The authors declare that there is no conflict of interests in thepaper
Acknowledgments
The authors are grateful for the gift of Monostroma nitidumfrom Kanetsu Sugiura Company Hamamatsu ShizuokaThey acknowledge the valuable discussion about the sensoryevaluation with Dr Bernhard Bruckner and thank all pan-elists for their support
References
[1] H Sugisawa K Nakamura and H Tamura ldquoThe aroma profileof the volatiles in marine green algae (Ulva pertusa)rdquo FoodReviews International vol 6 no 4 pp 573ndash589 1990
[2] S N Boopathy and K Kathiresan ldquoAnticancer drugs frommarine flora an overviewrdquo Journal of Oncology vol 2010Article ID 214186 18 pages 2010
[3] Food amp Agriculture Organization of the United Nations httpwwwfaoorgfoodfood-safety-qualityscientific-advicejecfajecfa-flaven
[4] T Kajiwara K Kodama A Hatanaka and K Matsui ldquoVolatilecompounds from Japanese marine brown algaerdquo in BioactiveVolatile Compounds from Plants vol 525 of ACS SymposiumSeries pp 103ndash120 1993
[5] Food Marketing amp Research Information Center httpwwwfmricorjptracenoriindexhtm
[6] P Poinot J Grua-Priol G Arvisenet et al ldquoOptimisation ofHS-SPME to study representativeness of partially baked breadodorant extractsrdquo Food Research International vol 40 no 9 pp1170ndash1184 2007
[7] D M A M Luykx and S M van Ruth ldquoAn overview of ana-lytical methods for determining the geographical origin of foodproductsrdquo Food Chemistry vol 107 no 2 pp 897ndash911 2008
8 The Scientific World Journal
[8] R Liu K Xiong Y Chao-Luo X Ze-Dai Z Min-Liu and WTong-Xue ldquoChanges in volatile compounds of a native Chinesechilli pepper (Capsicum frutescens var) during ripeningrdquo Inter-national Journal of Food Science amp Technology vol 44 no 12pp 2470ndash2475 2009
[9] I Silva S M Rocha and M A Coimbra ldquoHeadspace solidphase microextraction and gas chromatography-quadrupolemass spectrometry methodology for analysis of volatile com-pounds ofmarine salt as potential origin biomarkersrdquoAnalyticaChimica Acta vol 635 no 2 pp 167ndash174 2009
[10] K Tananuwong and S Lertsiri ldquoChanges in volatile aroma com-pounds of organic fragrant rice during storage under differentconditionsrdquo Journal of the Science of Food and Agriculture vol90 no 10 pp 1590ndash1596 2010
[11] K Kaseleht E Leitner and T Paalme ldquoDetermining aroma-active compounds in Kama flour using SPME-GCMS and GC-olfactometryrdquo Flavour and Fragrance Journal vol 26 no 2 pp122ndash128 2011
[12] A Prades R Assa M Dornier J P Pain and R BoulangerldquoCharacterisation of the volatile profile of coconut water fromfive varieties using an optimized HS-SPME-GC analysisrdquo Jour-nal of the Science of Food and Agriculture vol 92 pp 2471ndash24782012
[13] Flavornet httpwwwflavornetorg[14] S-P Hu and B S Pan ldquoModification of fish oil aroma using a
macroalgal lipoxygenaserdquo Journal of the American Oil ChemistsrsquoSociety vol 77 no 4 pp 343ndash348 2000
[15] Z Kamenarska A Ivanova R Stancheva et al ldquoVolatile com-pounds from some Black Sea red algae and their chemotaxo-nomic applicationrdquo Botanica Marina vol 49 no 1 pp 47ndash562006
[16] M E Hattab G Culioli L Piovetti S E Chitour and R VallsldquoComparison of various extraction methods for identificationand determination of volatile metabolites from the brown algaDictyopteris membranaceardquo Journal of Chromatography A vol1143 no 1-2 pp 1ndash7 2007
[17] V Gressler P Colepicolo and E Pinto ldquoUseful strategies foralgal volatile analysisrdquo Current Analytical Chemistry vol 5 no3 pp 271ndash292 2009
[18] R P Yu L P Wang S F Wu J S Che and Y M Liu ldquoAna-lysis of volatile compounds in Algal bloom water by gaschromatography-mass spectrometry and sniffingrdquo ChineseJournal of Analytical Chemistry vol 38 pp 1349ndash1352 2010
[19] A Rzama B Arreguy-San-Miguel and M Ettalibi ldquoLipidsmetabolites and essential oil from the green alga Chara vulgar-isrdquo Revue Marocaine des Sciences Agronomiques et Veterinairesvol 22 no 2 pp 65ndash70 2002
[20] M Okano and T Aratani ldquoConstituents in marine algae-Iseasonal variation of sterol hydrocarbon fatty acid and phytolfractions in Ulva pertusardquo Bulletin of the Japanese Society ofScientific Fisheries vol 45 pp 389ndash393 1979 (Japanese)
[21] Y H Hui Handbook of Fruit and Vegetable Flavors John Wileyamp Sons Hoboken NJ USA 2010
[22] P Fink E Von Elert and F Juttner ldquoVolatile foraging kair-omones in the littoral zone attraction of an herbivorous fresh-water gastropod to algal odorsrdquo Journal of Chemical Ecology vol32 no 9 pp 1867ndash1881 2006
[23] I Flament and G Ohloff ldquoVolatile constituents of algaeodoriferous constituents of seaweeds and structure of nor-terpenoids identified in Asakusa-Nori flavorrdquo in Proceedings ofthe 4th Weurman Flavour Research Symposium J Adda EdProgress in Flavor Research pp 281ndash300 Elsevier 1985
[24] M Kawakami ldquoIonone series compounds from beta-caroteneby thermal degradation in aqueous mediumrdquo Nippon Nogeika-gaku Kaishi vol 56 no 10 pp 917ndash921 1982 (Japanese)
[25] S Baldermann A N Mulyadi Z Yang et al ldquoApplication ofcentrifugal precipitation chromatography and high-speedcounter-current chromatography equipped with a spiral tubingsupport rotor for the isolation and partial characterization ofcarotenoid cleavage-like enzymes in Enteromorpha compressa(L) Neesrdquo Journal of Separation Science vol 34 no 19 pp2759ndash2764 2011
[26] R G Buttery R Teranishi L C Ling and J G TurnbaughldquoQuantitative and sensory studies on tomato paste volatilesrdquoJournal of Agricultural and Food Chemistry vol 38 no 1 pp336ndash340 1990
[27] F Ullrich and W Grosch ldquoIdentification of the most intenseodor compounds formed during autoxidation of methyl linole-nate at room temperaturerdquo Journal of the AmericanOil ChemistsSociety vol 65 no 8 pp 1313ndash1317 1988
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
The Scientific World Journal 7
Okayama2Okayama3
Okayama1
1
Tokushima2
Tokushima1
Tokushima3
Ehime3Ehime2
Ehime1
Shizuoka2Shizuoka1
Shizuoka3
0
0
2
2
4
4
6
6
8 10minus8 minus6
minus6
minus4
minus4
minus2
minus2
Observations (axes F1 and F2 6827)
F2
(20
14
)
F1 (4813)
Figure 5 Scoring plots of nontargeted profiling of green algaesamples of different origin by GC-MS-SPME The profiling wascarried out based on 41 peaks and detected corresponding peak arearatios Samples were independently analyzed in triplicate The datawere analyzed by PCA using XL-STAT 20132
respectively Moreover thermal degradation products of120573-carotene including 226-trimethylcyclohexanone benzal-dehyde 266-trimethyl-2-hydroxycyclohexanone 120573-cyclo-citral 56-epoxy-120573-ionone and dihydroactinidiolide werepreviously reported [24]
After the removal of undesirable material green algae aresun dried and packaged It might be speculated that similarreactions occur during the sun drying processing of greenalgae and may have a strong impact on the quality of algaeproducts The occurrence of apocarotenoids is one of themost important indicators of authenticity for Ulva proliferaUlva linza andMonostroma nitidum
Another class of aroma compounds the aliphatic acidmethyl esters including hexadecanoic acid methyl esterand methyl linolenate was abundant in algae from Shizuokaprefecture Methyl linolenate serves as aprecursor of (EZ)-35-octadien-2-one and is one of the most odor-activecompounds [27] It has been found in cod liver oil and Ulvapertusa and contributes to the melon-like odor In this study(E Z)-35-octadien-2-onewas detected in all samples andwasmore abundant in Ulva prolifera
To explain the overall characteristics of the four algaesamples further studies are necessary to elucidate the con-tribution of single components and identify unknown com-pounds
Multi-variant analysis of known components was per-formed on the mass spectral data to explain the overallcharacteristics of the differences among the samples PCAwas performed using a transformed data set consisting ofcorrelation matrix of 41 variables yielding in 11 eigenvectorsFive factors explained 9239 of the total variance indicatingthat a reduced number of volatile compounds could explainthe overall characteristics of the four different samplesFactor 1 explained 4813 of the total variance and factor 2explained 2014 of the total variance Both factors together
enable discrimination of the four algae samples fromdifferentbiological and geographical origins (Figure 5) It is interestingthat there are fewer differences in the volatile profiles ofsamples from close geographic origins such as Tokushimaand Okayama compared with samples which are furtheraway from each other for example Tokushima and EhimeFuture studies should be performed with a higher number ofreplicates and taking into account testing sets
4 Conclusions
The volatile profiles of different commercial Japanese greenalgae samples originating from Okayama TokushimaEhime and Shizuoka were described for the first timeMultivariate analysis enabled discrimination of the samplesbased on their botanical and geographical origin Hithertothe authenticity of these commercial products is based onpackage information and this study could form the analyticalbasis of authenticity studies of dried green algae samplesusing the SPME-GC-MS-method followed by multivarianteanalysis
Conflict of Interests
The authors declare that there is no conflict of interests in thepaper
Acknowledgments
The authors are grateful for the gift of Monostroma nitidumfrom Kanetsu Sugiura Company Hamamatsu ShizuokaThey acknowledge the valuable discussion about the sensoryevaluation with Dr Bernhard Bruckner and thank all pan-elists for their support
References
[1] H Sugisawa K Nakamura and H Tamura ldquoThe aroma profileof the volatiles in marine green algae (Ulva pertusa)rdquo FoodReviews International vol 6 no 4 pp 573ndash589 1990
[2] S N Boopathy and K Kathiresan ldquoAnticancer drugs frommarine flora an overviewrdquo Journal of Oncology vol 2010Article ID 214186 18 pages 2010
[3] Food amp Agriculture Organization of the United Nations httpwwwfaoorgfoodfood-safety-qualityscientific-advicejecfajecfa-flaven
[4] T Kajiwara K Kodama A Hatanaka and K Matsui ldquoVolatilecompounds from Japanese marine brown algaerdquo in BioactiveVolatile Compounds from Plants vol 525 of ACS SymposiumSeries pp 103ndash120 1993
[5] Food Marketing amp Research Information Center httpwwwfmricorjptracenoriindexhtm
[6] P Poinot J Grua-Priol G Arvisenet et al ldquoOptimisation ofHS-SPME to study representativeness of partially baked breadodorant extractsrdquo Food Research International vol 40 no 9 pp1170ndash1184 2007
[7] D M A M Luykx and S M van Ruth ldquoAn overview of ana-lytical methods for determining the geographical origin of foodproductsrdquo Food Chemistry vol 107 no 2 pp 897ndash911 2008
8 The Scientific World Journal
[8] R Liu K Xiong Y Chao-Luo X Ze-Dai Z Min-Liu and WTong-Xue ldquoChanges in volatile compounds of a native Chinesechilli pepper (Capsicum frutescens var) during ripeningrdquo Inter-national Journal of Food Science amp Technology vol 44 no 12pp 2470ndash2475 2009
[9] I Silva S M Rocha and M A Coimbra ldquoHeadspace solidphase microextraction and gas chromatography-quadrupolemass spectrometry methodology for analysis of volatile com-pounds ofmarine salt as potential origin biomarkersrdquoAnalyticaChimica Acta vol 635 no 2 pp 167ndash174 2009
[10] K Tananuwong and S Lertsiri ldquoChanges in volatile aroma com-pounds of organic fragrant rice during storage under differentconditionsrdquo Journal of the Science of Food and Agriculture vol90 no 10 pp 1590ndash1596 2010
[11] K Kaseleht E Leitner and T Paalme ldquoDetermining aroma-active compounds in Kama flour using SPME-GCMS and GC-olfactometryrdquo Flavour and Fragrance Journal vol 26 no 2 pp122ndash128 2011
[12] A Prades R Assa M Dornier J P Pain and R BoulangerldquoCharacterisation of the volatile profile of coconut water fromfive varieties using an optimized HS-SPME-GC analysisrdquo Jour-nal of the Science of Food and Agriculture vol 92 pp 2471ndash24782012
[13] Flavornet httpwwwflavornetorg[14] S-P Hu and B S Pan ldquoModification of fish oil aroma using a
macroalgal lipoxygenaserdquo Journal of the American Oil ChemistsrsquoSociety vol 77 no 4 pp 343ndash348 2000
[15] Z Kamenarska A Ivanova R Stancheva et al ldquoVolatile com-pounds from some Black Sea red algae and their chemotaxo-nomic applicationrdquo Botanica Marina vol 49 no 1 pp 47ndash562006
[16] M E Hattab G Culioli L Piovetti S E Chitour and R VallsldquoComparison of various extraction methods for identificationand determination of volatile metabolites from the brown algaDictyopteris membranaceardquo Journal of Chromatography A vol1143 no 1-2 pp 1ndash7 2007
[17] V Gressler P Colepicolo and E Pinto ldquoUseful strategies foralgal volatile analysisrdquo Current Analytical Chemistry vol 5 no3 pp 271ndash292 2009
[18] R P Yu L P Wang S F Wu J S Che and Y M Liu ldquoAna-lysis of volatile compounds in Algal bloom water by gaschromatography-mass spectrometry and sniffingrdquo ChineseJournal of Analytical Chemistry vol 38 pp 1349ndash1352 2010
[19] A Rzama B Arreguy-San-Miguel and M Ettalibi ldquoLipidsmetabolites and essential oil from the green alga Chara vulgar-isrdquo Revue Marocaine des Sciences Agronomiques et Veterinairesvol 22 no 2 pp 65ndash70 2002
[20] M Okano and T Aratani ldquoConstituents in marine algae-Iseasonal variation of sterol hydrocarbon fatty acid and phytolfractions in Ulva pertusardquo Bulletin of the Japanese Society ofScientific Fisheries vol 45 pp 389ndash393 1979 (Japanese)
[21] Y H Hui Handbook of Fruit and Vegetable Flavors John Wileyamp Sons Hoboken NJ USA 2010
[22] P Fink E Von Elert and F Juttner ldquoVolatile foraging kair-omones in the littoral zone attraction of an herbivorous fresh-water gastropod to algal odorsrdquo Journal of Chemical Ecology vol32 no 9 pp 1867ndash1881 2006
[23] I Flament and G Ohloff ldquoVolatile constituents of algaeodoriferous constituents of seaweeds and structure of nor-terpenoids identified in Asakusa-Nori flavorrdquo in Proceedings ofthe 4th Weurman Flavour Research Symposium J Adda EdProgress in Flavor Research pp 281ndash300 Elsevier 1985
[24] M Kawakami ldquoIonone series compounds from beta-caroteneby thermal degradation in aqueous mediumrdquo Nippon Nogeika-gaku Kaishi vol 56 no 10 pp 917ndash921 1982 (Japanese)
[25] S Baldermann A N Mulyadi Z Yang et al ldquoApplication ofcentrifugal precipitation chromatography and high-speedcounter-current chromatography equipped with a spiral tubingsupport rotor for the isolation and partial characterization ofcarotenoid cleavage-like enzymes in Enteromorpha compressa(L) Neesrdquo Journal of Separation Science vol 34 no 19 pp2759ndash2764 2011
[26] R G Buttery R Teranishi L C Ling and J G TurnbaughldquoQuantitative and sensory studies on tomato paste volatilesrdquoJournal of Agricultural and Food Chemistry vol 38 no 1 pp336ndash340 1990
[27] F Ullrich and W Grosch ldquoIdentification of the most intenseodor compounds formed during autoxidation of methyl linole-nate at room temperaturerdquo Journal of the AmericanOil ChemistsSociety vol 65 no 8 pp 1313ndash1317 1988
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
8 The Scientific World Journal
[8] R Liu K Xiong Y Chao-Luo X Ze-Dai Z Min-Liu and WTong-Xue ldquoChanges in volatile compounds of a native Chinesechilli pepper (Capsicum frutescens var) during ripeningrdquo Inter-national Journal of Food Science amp Technology vol 44 no 12pp 2470ndash2475 2009
[9] I Silva S M Rocha and M A Coimbra ldquoHeadspace solidphase microextraction and gas chromatography-quadrupolemass spectrometry methodology for analysis of volatile com-pounds ofmarine salt as potential origin biomarkersrdquoAnalyticaChimica Acta vol 635 no 2 pp 167ndash174 2009
[10] K Tananuwong and S Lertsiri ldquoChanges in volatile aroma com-pounds of organic fragrant rice during storage under differentconditionsrdquo Journal of the Science of Food and Agriculture vol90 no 10 pp 1590ndash1596 2010
[11] K Kaseleht E Leitner and T Paalme ldquoDetermining aroma-active compounds in Kama flour using SPME-GCMS and GC-olfactometryrdquo Flavour and Fragrance Journal vol 26 no 2 pp122ndash128 2011
[12] A Prades R Assa M Dornier J P Pain and R BoulangerldquoCharacterisation of the volatile profile of coconut water fromfive varieties using an optimized HS-SPME-GC analysisrdquo Jour-nal of the Science of Food and Agriculture vol 92 pp 2471ndash24782012
[13] Flavornet httpwwwflavornetorg[14] S-P Hu and B S Pan ldquoModification of fish oil aroma using a
macroalgal lipoxygenaserdquo Journal of the American Oil ChemistsrsquoSociety vol 77 no 4 pp 343ndash348 2000
[15] Z Kamenarska A Ivanova R Stancheva et al ldquoVolatile com-pounds from some Black Sea red algae and their chemotaxo-nomic applicationrdquo Botanica Marina vol 49 no 1 pp 47ndash562006
[16] M E Hattab G Culioli L Piovetti S E Chitour and R VallsldquoComparison of various extraction methods for identificationand determination of volatile metabolites from the brown algaDictyopteris membranaceardquo Journal of Chromatography A vol1143 no 1-2 pp 1ndash7 2007
[17] V Gressler P Colepicolo and E Pinto ldquoUseful strategies foralgal volatile analysisrdquo Current Analytical Chemistry vol 5 no3 pp 271ndash292 2009
[18] R P Yu L P Wang S F Wu J S Che and Y M Liu ldquoAna-lysis of volatile compounds in Algal bloom water by gaschromatography-mass spectrometry and sniffingrdquo ChineseJournal of Analytical Chemistry vol 38 pp 1349ndash1352 2010
[19] A Rzama B Arreguy-San-Miguel and M Ettalibi ldquoLipidsmetabolites and essential oil from the green alga Chara vulgar-isrdquo Revue Marocaine des Sciences Agronomiques et Veterinairesvol 22 no 2 pp 65ndash70 2002
[20] M Okano and T Aratani ldquoConstituents in marine algae-Iseasonal variation of sterol hydrocarbon fatty acid and phytolfractions in Ulva pertusardquo Bulletin of the Japanese Society ofScientific Fisheries vol 45 pp 389ndash393 1979 (Japanese)
[21] Y H Hui Handbook of Fruit and Vegetable Flavors John Wileyamp Sons Hoboken NJ USA 2010
[22] P Fink E Von Elert and F Juttner ldquoVolatile foraging kair-omones in the littoral zone attraction of an herbivorous fresh-water gastropod to algal odorsrdquo Journal of Chemical Ecology vol32 no 9 pp 1867ndash1881 2006
[23] I Flament and G Ohloff ldquoVolatile constituents of algaeodoriferous constituents of seaweeds and structure of nor-terpenoids identified in Asakusa-Nori flavorrdquo in Proceedings ofthe 4th Weurman Flavour Research Symposium J Adda EdProgress in Flavor Research pp 281ndash300 Elsevier 1985
[24] M Kawakami ldquoIonone series compounds from beta-caroteneby thermal degradation in aqueous mediumrdquo Nippon Nogeika-gaku Kaishi vol 56 no 10 pp 917ndash921 1982 (Japanese)
[25] S Baldermann A N Mulyadi Z Yang et al ldquoApplication ofcentrifugal precipitation chromatography and high-speedcounter-current chromatography equipped with a spiral tubingsupport rotor for the isolation and partial characterization ofcarotenoid cleavage-like enzymes in Enteromorpha compressa(L) Neesrdquo Journal of Separation Science vol 34 no 19 pp2759ndash2764 2011
[26] R G Buttery R Teranishi L C Ling and J G TurnbaughldquoQuantitative and sensory studies on tomato paste volatilesrdquoJournal of Agricultural and Food Chemistry vol 38 no 1 pp336ndash340 1990
[27] F Ullrich and W Grosch ldquoIdentification of the most intenseodor compounds formed during autoxidation of methyl linole-nate at room temperaturerdquo Journal of the AmericanOil ChemistsSociety vol 65 no 8 pp 1313ndash1317 1988
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of