Volatile profiles of aromatic and non-aromatic rice cultivars

13 Pages·2010·0.42 MB·English

FoodChemistry124(2011)501–513
ContentslistsavailableatScienceDirect
Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem
q
Volatile profiles of aromatic and non-aromatic rice cultivars using SPME/GC–MS
R.J. Bryant*, A.M. McClung
USDA-ARS,DaleBumpersNationalRiceResearchCenter,2890Hwy130E.,Stuttgart,AR72160,USA
a r t i c l e i n f o a b s t r a c t
Articlehistory: Rice(OryzasativaL.)isenjoyedbymanypeopleasastaplefoodbecauseofitsflavourandtexture.Some
Received2September2009 cultivars,likescentedrice,arepreferredoverothersduetotheirdistinctivearomaandflavour.Thevol-
Receivedinrevisedform30April2010 atileprofileofricehasbeenexploredbyotherinvestigators,someofwhomhavealsodeterminedacor-
Accepted16June2010
responding aroma using GC/olfactometry. However, little research has been done to determine if
differentaromaticricecultivarsproducedifferentflavourvolatilesthatwouldmakethemmoredesirable
thanotherswhencooked.Inthisstudy,sevenaromaticandtwonon-aromaticcultivarswereexamined
Keywords:
fortheirvolatileprofilesbothbeforeandafterstorageusingsolidphasemicroextraction(SPME)fibresin
Aroma
conjunction with gas chromatography/mass spectrometer (GC–MS). Ninety-three volatile compounds
Flavour
were identified, 64 of which had not been previously reported in rice. Differences were found in the
OryzasativaL.
Rice volatilecompoundsofaromaticandnon-aromaticricebesides2-acetyl-1-pyrroline(2-AP).Mostofthe
Scentedrice volatile compounds were present in freshly harvested rice and rice following storage, with very few
SPME new compounds being identified only after storage. Dellrose, an aromatic cultivar, and Cocodrie, a
GC/MS non-aromatic cultivar, had the most complex volatile profiles (over 64 volatiles). Sixteen compounds
Volatiles werefoundonlyinthearomaticcultivars,andsomevolatileswerefoundtobeuniquetospecificaro-
maticcultivars. However,no distinctive pattern was observed thatwould identifya cultivaras being
derivedfromBasmati,KhaoDawkMali105(i.e.jasmine),orothersourcesofaroma.Thisstudyshowed
that there is a great diversity of volatiles in both aromatic and non-aromatic rice cultivars and, with
furtherresearch,thismayleadtoabetterunderstandingofthecombinationofcompoundsthatgives
acultivarauniqueflavour.
PublishedbyElsevierLtd.
1.Introduction sensory attributes that distinguish these types of aromatic rice
cultivars in preference tests (Fitzgerald & Hall, 2008; Fitzgerald,
Rice(OryzasativaL.)isastaplefoodformanycountries.Unlike McCouch, & Hall, 2009). Currently, 2-acetyl-1-pyrroline (2-AP),
othergrains,e.g.wheat,corn,oroats,riceiscookedandconsumed which is a primary determinant of flavour in aromatic rice
asawholegrain.Aromaticricehasanaturalnutty,popcornflavour (Buttery,Ling,&Juliano,1982),istheonlyflavourcomponentthat
andaccountsfor86%ofimportsintotheUnitedStates(USDAEco- breedershavetheabilitytoselectfor.
nomicResearchService,2010).JasminericefromThailandandbas- Genetics, growing conditions, and post-harvest handling are
matiricefromPakistanandIndiaarethemainsourcesofaromatic factors which have been shown to affect the aroma and flavour
imports. Because this is an expanding market and imported jas- of rice (Champagne, 2008). There are several studies that have
mineandbasmatiricecultivarsarenotadaptedfordomesticpro- evaluated a number of rice cultivars from different genetic back-
duction, breeders have endeavoured to develop aromatic rice grounds (Bergman et al., 2000; Laguerre, Mestres, Davrieux,
cultivars that can be grown in the USA and favourably compete Ringuet, & Boulanger, 2007; Yang, Lee, Jeong, Kim, & Kays,
withimports.Jasmine,Basmatiand‘‘Della’’typeofaromaticculti- 2008a; Zeng, Zhang, Chen, Zhang, & Matsunaga, 2008) and rice
vars are distinguished by their grain shape, cooked rice texture, which has been stored under different conditions (Suzuki et al.,
andflavour(Bergman,Bhattacharya,&Ohtsubo,2004),andbreed- 1999;Tulyathan,Srisupattarawanich,&Suwanagul,2008;Widjaja,
ersusethesetraitsintheselectionofcultivarsfordifferentmarket Craske, & Wootton, 1996a; Wongpornchai, Dumri, Jongkaewwat-
segments.Studieshavedemonstratedthatconsumerscandiscern tana, & Siri, 2004; Zhou, Robards, Helliwell, & Blanchard, 2002).
A major focus has been on 2-AP, the primary volatile compound
inaromaticrice,however,lipidoxidationproductshavealsobeen
q Mentionofatrademarkorproprietaryproductinthisarticleissolelyforthe identifiedwhichareknowntohaveanegativeimpactonaccept-
purposeofprovidingspecificinformationanddoesnotimplyrecommendationor
ability (Champagne, 2008). The latter are compounds that may
endorsementbytheUnitedStatesDepartmentofAgriculture.
become more prevalent with the length of storage time or due
* Correspondingauthor.Tel.:[phone]x227;fax:[phone].
E-mailaddress:[email protected](R.J.Bryant). to poor post-harvest handling. The rice that is imported to the
0308-8146/$-seefrontmatterPublishedbyElsevierLtd.
doi:10.1016/j.foodchem.2010.06.061
502 R.J.Bryant,A.M.McClung/FoodChemistry124(2011)501–513
UnitedStatesissubjectedtomonthsofstorageandvariabletrans- including2-aminoacetophenoneandbis-(2-methyl-3-furyl)disul-
portconditions.Moreover,thebasmatiriceisfrequentlyagedfor phide,whichhadnotbeenpreviouslyreported.Zengetal.(2008)
atleastayearbeforeitismarketed(Fitzgeraldetal.,2009).Thus, foundthatthevolatileprofilechangedduringcooking.
the imported aromatic rice that is in the USA marketplace, may This study was conducted using SPME-GC/MS to evaluate the
have much different flavour profiles as compared to freshly har- volatile profiles of the rice cultivars that were produced in the
vested rice. Champagne (2008) noted that studies were needed same environment and were then subjected to different storage
usinglargersetsofricecultivarsthatwerehandledunderidentical timesandtemperatures.Thespecificobjectivesweretodetermine
pre-andpost-harvestconditionstoaddressflavourattributes. (1)ifvolatileprofilepatternsorcompoundsareuniquetojasmine,
Thevolatileprofileofricehasbeenexploredbyseveralinvesti- basmati,orDelladerivedcultivarsand(2)ifvolatileprofilesofcul-
gators,someofwhomhavealsodeterminedacorrespondingaro- tivarsdifferinresponsetostoragetimeandtemperature.
ma using gas chromatography (GC)/mass spectroscopy (MS)
olfactometry for most of the compounds detected (Jezussek, Juli-
2.Materialsandmethods
ano,&Schieberle,2002;Widjaja,Craske,&Wootton,1996b;Yang,
Shewfelt,Lee,&Keys,2008b;Zengetal.,2008).Asaresult,more
2.1.Samplepreparation
than200volatilecompoundshavebeenidentifiedinrice(Bergman
etal.,2000;Champagne,2008;Widjajaetal.,1996a,1996b;Yaj-
Sevenaromatic(Table1)andtwonon-aromatic(Cocodrieand
ima, Yani, Nakamura, Sakakibara, & Hayashi, 1979; Zeng et al.,
Wells)ricecultivarsweregrowninafieldexperimentattheDale
2008), some of which, e.g. 2-AP, 2-acetyl-pyrrole, a-pyrrolidone,
Bumpers National Rice Research Center/University of Arkansas
and pyridine, have been identified as enhancing the consumer
RiceResearchandExtensionCenternearStuttgart,ARin 2008.A
acceptability of rice, while other compounds, e.g. lipid oxidation
randomised complete block design with three replications was
products,suchashexanal,aceticacid,andpentanoicacid,canhave
used.Plotswereharvestedastheyapproached18–22%grainmois-
anegativeaffectonacceptability.
ture.Theroughricewasdriedto12%moistureusingaforcedair
The analysis of volatiles using solid phase microextraction
drier(29.4(cid:2)C),and25gofeachsamplewasdoublebaggedinZi-
(SPME)fibresinconjunctionwithGC/MShasproventobeaneffec-
ploc(cid:3)freezerbagsandstoredatthreedifferenttemperatures,30,
tive method since its development in the 1990s (Arthur & Paw-
4, and (cid:2)10(cid:2)C. Each sample was analysed for its volatile profile
liszyn,1990). Severaldifferentcombinationsofstationaryphases
priortostorageandevery30daysthereafterfor3months.Before
andfilmthicknessonfibresareavailabletochoosefrom(Supelco,
removing the samples from the freezer bags they were allowed
Bellefonte, PA), depending on the molecular weight of the com-
to equilibrate to room temperature (21–23(cid:2)C) overnight after
poundsofinterest.Smallermoleculesarebetterretainedusingfi-
whichtheyweredehulledandmilledto10–12%weightlossusing
bres containing Carboxen (CAR) or divinylbenzene (DVB) as a
aKettmill(KettElectricLaboratory,Ofa-Ku,Tokyo).
stationary phase, whereas, higher molecular weight compounds
desorb better from fibres which contain polydimethylsiloxane
2.2.GC–MSanalysis
(PDMS)asastationaryphase.Fibrescontainingacombinationof
stationaryphaseshavebeentestedandusedbyseveralinvestiga-
Asampleofwholemilledricekernels(20mg)wasplacedina
tors.Marsili(1999,2000)testedvariousfibresbutfoundthatthe
10ml vial; 20ll of ultra-pure (18.2MX) water containing 1ng
CAR/PDMScombinationextractedmoredifferenttypesofvolatiles
of 2,4,6-trimethylpyridine (TMP) (Sigma-Aldrich, St. Louis, MO)
when evaluating off-flavours in milk than other fibres. The DVB/
astheinternalstandardwasadded,andthevialwassealedwith
CAR/PCMS combination fibre has been used to analyse volatiles
aTeflonlinedmagneticcap.Thesampleswereplacedinanauto-
in rice (Grimm, Bergman, Delgado, & Bryant, 2001; Laguerre
samplertray,andweremaintainedatroomtemperatureuntilana-
et al., 2007; Zeng et al., 2008). This combination has been found
totrapagreaterrangeofvolatilecompoundswithdifferentpolar- lysed. The samples were preheated for 5min at 80(cid:2)C prior to
evaluation. A CTC Combipal SPME autosampler equipped with a
ities, e.g.ketones,alcohols,aldehydes,estersand terpenichydro-
heatedsampleshakerandaneedleheaterforthermalcleaningof
carbons, than other fibres, which is important when analysing
the SPME fibre was employed (Leap Technologies, Carrboro, NC).
complexcomponents,suchasricevolatiles(Ceva-Antunes,Bizzo,
Volatilecompoundswereadsorbedontoa1cm50/30divinylben-
Silva,Carvalho,&Antunes,2006;Mondelloetal.,2005).
zene/carboxen/polydimethylsiloxane stableflex fibre (carboxen/
DuetothesensitivityofSPME,contaminantsaregenerallyob-
DVB/PDMS) (Supelco, Bellefonte, PA) using an 18min adsorption
served.Themostpredominantpeaksdetectedwhenfibrescontain-
periodat80(cid:2)Cwhileshakingthesample.Blankswererunfollow-
ingPDMSareusedcontainingmassm/z73andm/z147,andhave
ingevery5thsampleasacontrol.
beenidentifiedassilylderivatives(Grimm,Champagne,&Oktsuba,
Samples were desorbed for 25s on a Varian Chrompack CP-
2002;Laguerreetal.,2007;Marsili,1999).Laguerreetal.(2007)la-
3800 gas chromatograph with a Saturn 2000 mass spectrometer
belledsixofthem(Si-1throughSi-6),identifyingthefirstthreeas
attached (GC–MS) (Varian Analytical Instruments, Walnut Creek,
hexamethyl-cyclotrisiloxane, octamethylcyclotetrasiloxane, and
CA). The injector temperature was held constant at 260(cid:2)C. The
decamethylcyclo-pentasiloxane,respectively.Grimmetal.(2002)
GCoventemperaturewasheldfor1minat50(cid:2)C,thenincreased
listedothercontaminantsidentifiedintheanalysisofricevolatiles
andtheirpossiblesources.
SPMEhas been reportedas a successful tool for screeningbut
not for the quantification of 2-AP in fragrant rice (Grimm et al., Table1
2001).IntheGrimmetal.(2001)study,SPMEgave<0.3%recovery, Sevenaromaticcultivars,theirparentalsource,andcountryoforigin.
withalargeerrorassociatedwiththeabsoluteconcentrationsof2-
Aromaticcultivars Parentalcultivar(country)
APinrice.Theaveragestandarddeviationwas11%withwhiterice,
Aromaticse2 Basmati370(India)
and20%errorwithbrownrice.Thestaticheadspacegaschroma-
Dellmati Domsiah(Iran)orDella(USA)
tography method developed by Sriseadka, Wongpornchai, and Dellrose Della(USA)
Kitsawatpaiboon(2006)wasvalidatedforthequantitativeanalysis IAC600 Unknown(Japan)
of2-AP.Widjajaetal.(1996a)foundcamphor,2-methylbenzalde- Jasmine85 KhaoDawkMali105(Thailand)
hyde and butyl benzoate in Australian rice, which had not been JES KhaoDawkMali105(Thailand)
Sierra Della(USA)orBasmati370(India)
previously reported. Jezussek et al. (2002) found 11 compounds
R.J.Bryant,A.M.McClung/FoodChemistry124(2011)501–513 503
Fig.1. Typicalchromatogramof(A)aromaticriceand(B)non-aromaticricewithoverlayofselectedions(m/z83,100%;m/z82,45%;m/z111,28%)usedforidentificationof
2-AP.
to 260(cid:2)C at 5(cid:2)C/min, and then held at 260(cid:2)C for 4min. A carrier gas under a constant flow of 28.6cm/s (1ml/min), in the
30m(cid:3)0.25mm ID with a 0.25lm thickness of 5% diphenyl – splitless mode. The total GC cycle time consisted of a 47.0min
95%dimethylpolysilosanecrossbondedliquidphase(DB-5)capil- run and a 5min re-stabilisation time. The MS was operated in
larycolumnwasused,withresearchgradehelium(99.999%)asthe thescanmodefromm/z40to650.Eachcompoundwasidentified
504 R.J.Bryant,A.M.McClung/FoodChemistry124(2011)501–513
bythepresenceofselectedionsandtheirratio(Fig.1),andbycom- Table2
paringtheMSspectratothereferencespectraintheNationalInsti- SiloxanederivativesdetectedusingSPMEGC/MS.
tute of Standards and Technology (NIST, ver. 2.0f, 2008) mass Majorsilosane Chemicalname Retention
spectral database. A typical chromatogram showing the location derivatives time
of2-APandTMPisshowninFig.2a. S1 Dimethylsilanediol 3.531
Trans-2(clorovinyl)dimethylylethoxysilane 3.765
S2 Octamethylcyclotetrasiloxane 8.159
3.Resultsanddiscussion
2,5-Bis(trimethylsily)oxybenzaldehyde 11.5
S3 [[4-[1,2-bis(trimethylsilyl)oxy]ethyl]-1,2- 12.592
Althoughquantitativedatawerenotdeterminedinthisstudy, phenylene)bis(oxy)bis(trimethyl)]silane 12.651
the absence of a compound indicates that it is absent or present decamethylcyclopentasiloxane 15.399
dimethyl(dimethyl(dimethyl(2- 16
in concentrations below the detection limits. The combination of
isopropylphenoxy)siolyloxy)(2- 16.439
volatilecompoundsdetectedinricepriortostoragegivesanindi- isopropylphenoxy)silane3,5-dibutoxy- 17.295
cationofthedifferencesthatmayexistintheflavourandaromaof 1,1,1,7,7,7-hexamethyl-3,5
freshly harvested rice. After storage, the presence or absence of bis(trimethylsiloxy)tetrasiloxane7-chloro-1,3-
dihydro-5-phenyl-1-(trimethylsilyl)-2H,-1,4
volatilecompoundsmayreflectachangeintheflavourandaroma
benzodiazepin-2-one2-[trimethylsily)amino]-
duetoaging.Elevenaldehydes,15alkanes,10alkenes,10ketones,
3-[trimethysilyl)oxy]estra-1,3,5(10)-trien-17-
19 alcohols, 4 amines, 5 acids, and 19 miscellaneous compounds one
wereidentified.Table3liststhecompoundsthathavebeenprevi- S4 Dodecamethylcyclohexasiloxane 17.476
ously identified and/or aromas that have been detected using a S5 Tetradecamethylcycloheptasiloxane 21.603
S6 Hexadecamethylcyclooctacilosane 25.452
sniffing port (Widjaja et al., 1996a, 1996b; Jezussek et al., 2002;
S7 2,3-Bis(trimethylsilyl)oxy-estra-1,3,5(10)- 28.975
Yang et al., 2008a, 2008b). The internal standard TMP was found trien-17-one
ineachsample, and2-APwas foundin allaromaticsamples,but S8 Eicosamethylcyclodecasiloxane 31.8
not in the non-aromatic cultivars (Wells and Cocodrie), as ex-
pected. 2-AP gives rice a pleasant sweet popcorn flavour, which
is characteristic of all aromatic rices, but is missing in non-aro-
maticrice(Butteryetal.,1982). Sevenscentedcultivarswereevaluated,andnoclearpatternof
AsreportedbyotherinvestigatorswhousedSPMEfibrescon- volatileprofilesemergedfortheBasmati,Della,orKhaoDawkMali
taining PDMS (Grimm et al., 2002; Laguerre et al., 2007; Marsili, 105 derived cultivars(Table 4a–g). Other investigators have con-
1999),siloxanederivativescausedbythefibrewerethemostpre- ducted comparative research on both scented and non-aromatic
dominantpeaks seenin thechromatogram(Fig. 2b).A list ofthe rice cultivars with similar results. Widjaja et al. (1996a, 1996b)
major and minor siloxane derivatives detected in this study are comparedthevolatilecomponentsofcookedmilledricecultivars,
shown in Table 2. Other contaminants were also detected in this andfoundnodifferencesinthevolatilecompoundspresent,only
study, some of which have been reported by other investigators, inthequantity.Jezusseketal.(2002)comparedthevolatilecom-
suchas butylatedhydroxytoluene(BHT),methoxy-phenyl-oxime, ponents of cooked brown (one non-aromatic and three scented)
anddiethylphthalate(Grimmetal.,2002).Somecontaminantsab- rices,andalsofoundthatnoonecompoundorsetofcompounds
sorbedfromthecontainer(e.g.plasticorclothbags)duringstorage definedacultivar,onlytheconcentration.Zengetal.(2008)com-
maygivethericeanoff-flavouriftheconcentrationishighenough. paredthevolatilecompoundsofthreenon-aromaticricesatfour
All93volatilecompoundswereidentifiedinthesamples;theyare differenttimesduringcooking.Theyfoundthatalthoughtheculti-
showninTable3,alongwiththeirretentiontimes. varsdifferedinthepresenceoffattyacidesters,themajordiffer-
Fig.2. Typicalchromatogram:(A)riceextractusingSPME/GC–MSshowingthelocationof2-APandtheinternalstandardTMP;(B)blankshowingmajorsiloxane(seeTable
2).
R.J.Bryant,A.M.McClung/FoodChemistry124(2011)501–513 505
Table3
Volatilecompoundsdetectedinricecultivars.a,b
Refs.c Chemicalname Aroma Retentiontime(min)
Propiolonitrile 2.31
3-Dimethyl-2-(4-chlorphenyl)-thioacrylamide 2.35
X 2,5 Pentanal Woodyandfruity 2.80
1-Chloro-3-methylbutane 3.59
X 1–5 Hexanal Greentomato,green,grass-like 4.17
1-Chloro-3,5-bis(1,1-dimethylethyl)2-(2-propenyloxy)benzene 4.29
X 2,4,5 Hexanol Herbaceous 5.50
5-Methyl-2-hexanone 6.00
X+ 3 Methoxy-phenyl-oxime 6.25
X 1,2,4,5 Heptanal Fatty,rancid,fruity 6.26
Pyrolo[3,2-d]pyrimidin-2,4(1H,3H)-dione 6.42
5-Amino-3,6-dihydro-3-imino-1(2H)pyrazineacetonitrile 6.78
2-Butyl-1,2-azaborolidine 6.80
X 1,2,4,5 2-AP Popcorn,sweet,andpleasant 6.96
+ 2-Chloroethylhexylesterisophthalic 7.28
2-Chloro-3-methyl-1-phenyl-1-butanone 7.90
Tetrahydro-2,2,4,4-tetramethylfuran 8.10
N,N-dinonyl-2-phenylthioethylamine 8.20
X 1,4,5 1-Octen-3-ol Mushroom 8.35
6-Methyl-5-hepten-2-one Banana-like 8.46
X 1–5 2-Pentylfuran Floral,fruit,nutty,andbean 8.61
X 1–5 Octanal Citrus,fruity,floral,andfatty 9.03
+ 2-Methyl-1,3-pentanediol 9.15
2,2-Dihydroxy-1-phenyl-ethanone 9.47
X 2 2-Ethyl-1-hexanol 9.75
5-Methy-3-Hepten-2-one 10.05
X 1–5 2-Ocetenal(E) Nutty,green,andfatty 10.65
1-(1H-pyrrol-2-yl)-ethanone 10.79
3,5-Dimethyl-1-hexene 10.99
X+ 3 2-Methoxyphenol Smoky 11.45
(E)-2-Nonen-1-ol 11.93
X 1–5 (E)-2-Nonenal Beany,cucumber,fatty,woody,andtallowy 13.60
Nonene 13.90
X+ 1,2,4 Naphthalene Naphthalene 14.43
7-Chloro-4-hydroxyquinoline 14.49
O-decylhydroxamine 14.67
2-Methyldecane 14.70
2-Decen-1-ol Citrusandrose 14.90
Cyclodecanol 14.91
[(1-Methylethyl)thio]cyclohexane 14.97
4Methyl-2-pentyne 15.02
N,N-dimethylchloestan-7-amine 16.04
X 2 Benzothiazole Slightlysweet 16.53
1-Tetradecyne 16.90
X 1–5 Indole Mothball,floral,sweet,andburnt 17.42
Pentadecanal 17.70
Isobutylnonylesteroxalicacid 17.86
4-Cyclohexyl-dodecane 18.66
2-Hexyl-1-decanol 18.70
2-Butyl-1-octenal 19.30
X 2 2-Butyl-2-octenal 19.42
7-Tetradecene 19.91
Dotriacontane 20.14
+ 2,4,7,9-Tetramethyl-5-decyn-4,7-diol 20.36
Z-10-pentadecen-1-ol 20.40
3-Tridecene 20.42
Octadecyne 20.50
5-Ethyl-4-methyl-2-phenyl-1,3-dioxane 21.19
6-Methyl-octadecane 21.28
6,10-Dimethyl-5,9undecadien-2-one 21.40
2,6-Bis(1,1-dimethylethyl)-2,5-cyclohexadiene-1,4-dione 21.70
2-Methyl-hexadecanal 21.90
X 5 1-Hexadecanol 22.08
17-Pentatricontene 22.42
1-Docosene 22.46
X+ 2 Butylatedhydroxytoulene 22.75
+ 2,4-Bis(1,1-dimethylethyl)-phenol 22.87
n-Nonadecanol 23.02
Pentacontonal 23.03
X 2 Nonadecane 23.80
3,5-Di-tert-butyl-4-hydroxybenzaldehyde 23.99
X 2 2-Hexyl-1-octanol 24.17
2,2,4-Trimethyl-3-carboxyisopropyl,isobutylesterpentanoicacid 24.78
X+ 1,2 Diethylphthalate 24.88
(continuedonnextpage)
506 R.J.Bryant,A.M.McClung/FoodChemistry124(2011)501–513
Table3(continued)
Refs.c Chemicalname Aroma Retentiontime(min)
X 2 Heptadecane 25.57
1-Chloro-nonadecane 25.81
Hexadecylester,2,6-difluro-3-methylbenzoicacid 26.06
2-Butyl-1-octanol 26.10
Tritetracontane 26.20
3,5,24-Trimethyltetracontane 26.22
+ Eicosanol 26.36
Decylbenzene 26.84
2-Hexadecanol 27.00
4-Acetoxypentadecane 27.04
2-Methyl-1-hexadecanol 27.09
Isobutylhexadecylesteroxalicacid 27.65
Hexylpentadecylester-sulphurousacid 28.40
Heptylcyclohexane 28.65
n-Heptadecylcyclohexane 28.72
2-Hexyl-decanol 29.46
1-Hexacosene 30.80
7,9-Di-tert-butyl-1-oxaspiro-(4,5)deca-6,9-diene-2,8-dione 31.67
a X=previouslyidentifiedcompoundsinrice.
b +=Putativecontaminants.
c Refs.=(1)Widjajaetal.(1996a,1996b),(2)Grimmetal.(2002),(3)Jezusseketal.(2002),(4)Yangetal.(2008a,2008b),and(5)Zengetal.(2008).
Table4a
Ketonesdetectedinfreshlyharvestedriceandfollowingstorage.a
Ketones
5- Pyrolo[3,2- 2-Chloro-3- 6- 2,2- 5- 1-(1H- 6,10- 2,6-Bis(1,1- 7,9-Di-tert-butyl-1-
Methyl- d]pyrimidin- methyl-1- Methyl- Dihydroxy- Methy- pyrrol-2- Dimethyl- dimethylethyl)- oxaspiro-(4,5)deca-
2- 2,4(1H,3H)- phenyl-1- 5- 1-phenyl- 3- yl)- 5,9 2,5- 6,9-diene,2,8-dione
hexanone dione butanone hepten- ethanone hepten- ethanone undecadien- cyclohexadiene-
2-one 2-one 2-one 1,4-dione
4a-1 4a-2 4a-3 4a-4 4a-5 4a-6 4a-7 4a-8 4a-9 4a-10
Aromatic X X X X X X
se2
30(cid:2)C F/S/T F S F/S/T F/S/T
4(cid:2)C F/S/T F/S/T F/S F/S/T F/S/T
(cid:2)10(cid:2)C F/S/T F/S/T F/S/T F/S/T
Dellmati X X X X X
30(cid:2)C F/S/T S/T S/T F/S/T S/T S/T
4(cid:2)C F/S/T F S F/S/T T F/S/T
(cid:2)10(cid:2)C F/S/T F/S/T F/S/T
Dellrose X X X X
30(cid:2)C F/S/T F/S/T F/S/T F/S/T F/S/T
4(cid:2)C F/S/T S/T F S/T
(cid:2)10(cid:2)C F/S/T F/S/T
IAC600 X X X X
30(cid:2)C F/S/T F/S S/T F/S/T
4(cid:2)C F/S/T F S/T F/S/T
(cid:2)10(cid:2)C F/S/T F F/S/T F/S
Jasmine X X X X X X X
85
30(cid:2)C F/S/T F/S/T F/S/T F F/S/T F/S/T F/S/T
4(cid:2)C F/S/T F F/S/T F/S/T
(cid:2)10(cid:2)C F/S/T F/S/T
JES X X X X X X
30(cid:2)C F/S/T T F S F/S/T S/T S/T
4(cid:2)C F/S/T F/S/T S/T
(cid:2)10(cid:2)C F/S/T T F/S/T F/S/T F/S/T
Sierra X X X X
30(cid:2)C F/S/T F/S/T S F/S/T S/T
4(cid:2)C F/S/T F F/S/T F/S/T
(cid:2)10(cid:2)C F/S/T F/S/T F/S/T
Cocodrie X X X X X X
30(cid:2)C F/S/T F/S/T F/S/T F/S/T F/S F/S/T S/T S/T
4(cid:2)C F/S/T F/S/T F/S/T F/S/T
(cid:2)10(cid:2)C T F/S/T F T F/S/T S/T
Wells X X X X X X
30(cid:2)C F/S/T F/S/T F F/S/T F/S/T
4(cid:2)C F/S/T F/S/T F F/S/T F/S/T
(cid:2)10(cid:2)C F/S/T T F/S/T F/S/T F/T
a X=priortostorage,F=firstmonth,S=secondmonth,andT=thirdmonth.
R.J.Bryant,A.M.McClung/FoodChemistry124(2011)501–513 507
2-Hexyl-decanol 4b-19 X F/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TX F/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TX F/S/TF/S/T
2-Methyl-1-hexadecanol 4b-18 X F/S/T XF/S/T S/T XF/S/TF/S/T X S/T X F/S/T
ol
n
2-Hexadeca 4b-17 XF/S/T X F/S/T X F/S/TF/S/TX S/TF/S/T
ol
n
#Eicosa 4b-16 X F/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TX F/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TX F/S/TF/S/T
2-Hexyl-1-octanol 4b-15 X F/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/T F/S/TS/TF/TX F/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TS/TF/S/TXF/S/TF/S/TF/S/TX F/S/T
ol
n
n-Nonadeca 4b-14 S/T XF/S/TF/S/TF X F/S/TF/S/TXF/S/T
1-hyl)-
#2,4-Bis(1,dimethyletphenol 4b-13 X F/S/TFF/S/TXF F/S/TXF/S/TF/S/TF/S/TX F/S/TF/S/TX F/S/TSF/S/TX F/S/TF/S/TXF/S/T XF/S/TF/S/TFX F/S
2-Butyloctanol 4b-12 XF/S/T X F/S/T XF/S/TS/T X F/S/TF/S/T
ol
n
1-Hexadeca 4b-11 X S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXSF/TF/S/TX F/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/SF/S/TXF/S/TF/S/TF/S/T
n-
Z-10-pentadece1-ol 4b-10 F/S/T X F/S/T XF/S/T F/S/TX F/S/T XF/S/TF/S/TF/S/TXF/S/TF/S/T S/T
#2,4,7,9-Tetramethyl-5-decyn-4,7-diol 4b-9 X F/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXS/TF/S/TF/S/TX F/S/TF/S/TF/S/TXF/S/TS/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TS/TXF/S/TF/S/TF/S/T nts.
nol mina
Cyclodeca2-Decen-1-ol 4b-74b-8 X F/S/TF/S/T XXF/S/TF/S/TF/S/TXXF/S/TF/S/TF/S/TXF/S F/S/TX F/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/T #=putativeconta
d
astorage. (E)-2-Nonen-1-ol 4b-6 X F/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TX F/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TX F/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/T month;an
following #2-Methoxyphenol 4b-5 F/S/T T=third
freshlyharvestedriceand 2-Ethyl-#2-Methyl-1-1,3-hexanolpentanediol 4b-34b-4 XX TF/S/TF/S/TF/S/TS/TF/S/TXTF/S/TS/TTSF/S/TXS/TF/S/TS/TSTF/S/TXXS/TF/S/TF/S/TF/S/TF/S/TF/S/TX F/S/TS/TS/TS/TF/S/TXTF/S/TS/TF/S/TS/TF/S/TXTF/S/TS/TS/TF/S/TXXS/TS/TF/S/TTF/S/TXS/TF/S/T S/TF/S/T month,S=secondmonth,
phenolsdetectedin Alcohols Hexanol1-Octen-3-ol 4b-14b-2 X F/S/TF/S/TSF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TFF/S/TX F/S/TF/S/TF/S/TXF/S/TTF/S/TF/S/TXF/S/TF/S/TF/S/TXXF/S/TF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/T tostorage,F=first
Table4bAlcoholsand Aromaticse230C(cid:2)4C(cid:2)10C(cid:2)(cid:2)Dellmati30C(cid:2)4C(cid:2)10C(cid:2)(cid:2)Dellrose30C(cid:2)4C(cid:2)10C(cid:2)(cid:2)IAC60030C(cid:2)4C(cid:2)10C(cid:2)(cid:2)Jasmine85C30(cid:2)4C(cid:2)10C(cid:2)(cid:2)JES30C(cid:2)4C(cid:2)10C(cid:2)(cid:2)Sierra30C(cid:2)4C(cid:2)10C(cid:2)(cid:2)Cocodrie30C(cid:2)4C(cid:2)10C(cid:2)(cid:2)Wells30C(cid:2)4C(cid:2)10C(cid:2)(cid:2) aX=prior
508 R.J.Bryant,A.M.McClung/FoodChemistry124(2011)501–513
Table4c
Acidsandaminesdetectedinfreshlyharvestedriceandfollowingstorage.a
Acids Amines
Isobutyl 2,2,4-Trimethyl-3- Hexadecylester, Isobutyl Hexylpentadecyl N,N-dinonyl- N-methoxy O-decyl N,N-
nonyl carboxyisopropyl, 2,6-difluro-3- hexadecyl ester- 2-phenylthio methanamine hydroxamine dimethyl
ester isobutylester methylbenzoic esteroxalic sulphurousacid ethylamine chloestan-
oxalicacid pentanoicacid acid acid 7-amine
4c-1 4c-2 4c-3 4c-4 4c-5 4c-6 4c-7 4c-8 4c-9
Aromatic X X X X X
se2
30(cid:2)C F/S/T F/S/T F/S/T S/T F/S/T
4(cid:2)C F/S/T F/S/T F/S/T F/S/T F/S/T S/T
(cid:2)10(cid:2)C F F/S/T F/S/T F/S/T
Dellmati X X X X X
30(cid:2)C F/S/T F/S/T S/T S/T
4(cid:2)C S/T F/S/T F/S/T F/S/T
(cid:2)10(cid:2)C F/S/T F/S/T F/S/T F/S/T
Dellrose X X X X X X
30(cid:2)C F/S/T F/S/T S/T F/S/T
4(cid:2)C F/S/T S/T F/S/T
(cid:2)10(cid:2)C F/S/T F/S/T F/S/T F/S/T
IAC600 X X X
30(cid:2)C S F/S/T F/S/T F/S/T
4(cid:2)C F/S/T F/S/T S/T F/S/T
(cid:2)10(cid:2)C F T/S F/S/T
Jasmine X X X X X X
85
30(cid:2)C F/S/T F/S/T F/S/T
4(cid:2)C F/S/T F/S/T F/S/T F/S/T
(cid:2)10(cid:2)C F/S/T F/S/T F/S/T F/S/T
JES X X X X X X X
30(cid:2)C F/S/T F/S/T F/S/T S/T F F/S/T
4(cid:2)C F/S/T F/S/T F/S/T F/S/T F/S/T F/S/T
(cid:2)10(cid:2)C F/S/T F/S/T F/S/T F/S/T F/S/T F/S/T
Sierra X X X X X
30(cid:2)C F/S/T F/S/T F/S/T F/S/T
4(cid:2)C F/S/T F/S/T S/T F/S/T
(cid:2)10(cid:2)C F/S/T F/S/T F/S/T
Cocodrie X X X X X X X
30(cid:2)C F/S/T F/S/T F/S/T
4(cid:2)C F/S/T F/S/T F/S/T F/S/T S/T F/S/T
(cid:2)10(cid:2)C F/S/T F/S/T S/T F/S/T F/S/T F/S/T
Wells X X X X X
30(cid:2)C F/S/T F/S/T F/S/T
4(cid:2)C F/S/T F/S/T F/S/T
(cid:2)10(cid:2)C F/S/T F/S/T F/S/T F/S/T
a X=priortostorage,F=firstmonth,S=secondmonth,T=thirdmonth;and#=putativecontaminants.
encewasthetimewhichthecompoundappearedduringcooking, ketone derivatives (7) of the aromatic rices, and all of them
and its concentration. In our study, the non-aromatic cultivar remained present at 30(cid:2)C, while at 4(cid:2)C only four (#4a-2, 4a-5,
Cocodriewasobservedtohavethehighestnumber(69)ofvolatile 4a-7, and 4a-8) were detected, and at (cid:2)10(cid:2)C only 2 (#4a-2 and
compounds, and that all but seven of these were present in the 4a-8)weredetected.However,asimilarresponsetostoragecondi-
freshly harvested samples. Twelve of the 14 volatiles that have tionswasnotobservedforthesesamecompoundsinotherculti-
beenassociatedwithflavours,butarenotcontaminants,werede- vars. Jasmine 85 and Cocodrie were the only two cultivars that
tectedinCocodrie.Incontrast,Wellshadthefewest(51)volatile contained 5-methy-3-hepten-2-one, which was found only in
compoundsofallthecultivarstested,andthefewestnumber(5) freshlyharvestedriceandafterstorageat30(cid:2)C.Allcultivarsthat
ofvolatilesassociatedwithflavour.Ofthearomaticcultivars,Dell- contained6-methyl-5-hepten-2-one,alsocontained6,10-demeth-
rose had the most complex volatile profile (65 compounds), and yl-5,9 undecadien-2-one, except for Dellrose. Though previously
likeAromaticse2andJES,italsohadalargenumberofthevolatiles reported in rice, no aroma has been associated with 6,10-
associatedwithflavour(10–11compounds). dimethyl-5,9 undecadien-2-one (Grimmet al.,2002). In the non-
Similarto2-AP,ketonescangiveapleasantaroma(e.g.banana- aromatic cultivars, Wells and Cocodrie contained six and eight
like,fruity,caramel-like,nutty)torice.Ofthe10ketonesdetected ketone derivatives, respectively, all of which were also found in
(Table4a),#4a-2,4a-8,and4a-10werefoundinmostcultivarsand the aromatic group. 7,9-Di-tert-butyl-1-oxaspiro-(4,5)deca-6,
storageconditions.Ketone#4a-4,whichisassociatedwithabana- 9-diene,2,8-dione was detected at all storage temperatures in all
na-like flavour (Zeng et al., 2008), was observed in Cocodrie and cultivarsexcept Jasmine 85. 2-Chloro-3-methyl-1-phenyl-1-buta-
Wells across all storage treatments, but was found only sporadi- nonewasonlydetectedinJasmine85priortostorage,andinthe
cally in the aromatic cultivars. Four of the ketones (#4a-1, 4a-3, 30(cid:2)C treatment, while 5-methy-2-hexanone was unique to Dell-
4a-6, and 4a-9) were rarely detected among any of the cultivar- rose at 30(cid:2)C. These two ketones help define a distinctive profile
storage combinations, suggesting that they would have little for these cultivars, but neither of these compounds have been
importance in flavour. Prior to storage, Jasmine 85 had the most linkedwithflavour.
R.J.Bryant,A.M.McClung/FoodChemistry124(2011)501–513 509
Table4d
Aldehydesdetectedinfreshlyharvestedriceandfollowingstorage.a
Aldehydes
Pentanal Hexanal Heptanal Octanal 2- (E)-2- Pentadecanal 2-Butyl-1- 2-Butyl-2- 2-Methyl- Pentacontonal
Ocetenal nonenal octenal octenal hexadecanal
(E)
4d-1 4d-2 4d-3 4d-4 4d-5 4d-6 4d-7 4d-8 4d-9 4d-10 4d-11
Aromatic X X X X X X
se2
30(cid:2)C F/S/T F/S S/T F/S/T F/S/T S/T
4(cid:2)C S F/S F/S/T F S/T
(cid:2)10(cid:2)C S/T F/S/T T F/S/T F/S/T F/S/T F/S/T
Dellmati X X X X X X X X
30(cid:2)C F/S/T F/S/T F/S/T F/S/T F/S/T F/S/T S/T
4(cid:2)C F/S/T S/T F/S/T S/T
(cid:2)10(cid:2)C F/S/T F/S/T F/S/T F/S/T F/S/T F/S/T F/S/T
Dellrose X X X X X X X X
30(cid:2)C S/T F/S/T F/S/T S/T F/S/T F/S/T F/S/T
4(cid:2)C F/S/T F/S/T F/S/T F/S/T F/S/T S/T S/T
(cid:2)10(cid:2)C F/S/T F/S/T F/S/T F/S/T F/S/T F/S
IAC600 X X X X
30(cid:2)C S/T F/S/T F/S/T
4(cid:2)C T F/S/T F/S/T
(cid:2)10(cid:2)C T
Jasmine X X X
85
30(cid:2)C F/S/T F/S/T
4(cid:2)C F/S/T F/S/T
(cid:2)10(cid:2)C F F/S/T F/S/T
JES X X X X X X X
30(cid:2)C F/S/T F/T S/T F/S/T F/S/T
4(cid:2)C F/S/T F/S/T F/S/T F/S/T S/T F/S/T
(cid:2)10(cid:2)C F/S/T S F/S/T F/S/T F/S/T F/S/T
Sierra X X
30(cid:2)C S/T S S/T F/S/T S/T
4(cid:2)C T S/T F/S/T
(cid:2)10(cid:2)C F/T F/S/T F/S/T F
Cocodrie X X X X X X X X X
30(cid:2)C F/S/T F/S/T F/S/T F/S/T F/S/T F/S/T F/S/T F/S/T F/S/T
4(cid:2)C F/S/T F/S/T F/S/T F/S/T F/S/T F/S/T
(cid:2)10(cid:2)C F/S/T F/S F/S/T S F/S/T F/S/T F/S/T
Wells X X X X X
30(cid:2)C F/S/T F/S/T S/T
4(cid:2)C F/S/T F/S/T F/S/T
(cid:2)10(cid:2)C F/S/T F/S/T F/S/T F/S/T F/S/T F/S/T
a X=priortostorage,F=firstmonth,S=secondmonth,andT=thirdmonth.
Alcohols, phenols, and amines can give a pleasant aroma like tions were observed to possess acids #4c-2, 4c-3, and 4c-4 and
sweet, floral, or fruity to rice. Of the 19 alcohol derivatives de- theamine#4c-8(Table4c).Acid#4c-1wasfoundinallcultivars
tected, five are believed to be contaminants (#4b-3, 4b-5, 4b-9, except Sierra, whereas acid #4c-5 was unique to Aromatic se2.
4b-13,and4b-16)(Table4b).Elevenwerecommonlyfoundinboth JES was the only cultivar to possess all four amines, and it was
scentedandnon-aromaticcultivars,suggestingthattheymaynot the only one where N-methoxy methanamine was detected. Of
be useful in distinguishing among cultivars. The most alcohols thefouraminesmeasured,IAC600andWellscontainedonlyO-de-
(17) were observed in samples of JES, whereas, the fewest (11) cylhydroxamine.
were detected in Wells. Hexanols (#4b-1) which are associated Aldehydes,alkanes,andalkenes,whichareassociatedwithlipid
withagreenorgrass-likeflavourwerefoundinallbuttwosam- breakdownproductscanbelinkedwithflavourslikegrassy,fatty,
ples,and#4b-3,whichisnotassociatedwithaflavourandisre- andsoapy(Table4d–f).However,dependingontheconcentrations
ported as a contaminant, was detected in all cultivars generally ofthesecompounds,theymayhaveapleasantorobjectionablear-
after two or more months of storage. Of the seven alcohols that oma.Generally,themorelipidbreakdownproducts,themorelikely
wereuncommon,#4b-5,4b-7,4b-14,and4b-17wereonlyfound thericeistohavearancidodourandoff-flavour.Thepresenceof
inaromatics.IAC600wastheonlycultivartopossess#4b-5,which hexanal has been used to determine off-flavour in rice (Bergman
isassociatedwithasmokyflavour,butthiswasobservedonlyun- etal., 2000; Wongpornchai etal., 2004). Of the11 aldehydesde-
der(cid:2)10(cid:2)Cstorageconditions.TheDellmatiandDellrosesamples tected,#4d-2,4d-4,4d-6,4d-7,and4d-10werecommonlyfound,
that were freshly harvested and then stored under low tempera- andsix(#4d-1,4d-2,4d-3,4d-4,4d-5,and4d-6,)wereassociated
tures, contained 2-decen-1-ol, which has a citrus or rose aroma. withflavours(Table4d).Infreshlyharvestedrice,octanalwasde-
1-Octen-3-ol (#4b-2), which is linked with a raw mushroom fla- tectedinallcultivarsandhexanalwasdetectedinallexceptSierra
vour, was found in two scented cultivars, the Aromatic se2 and indicating that lipid breakdown products are produced quickly
JES, but only when stored for 2months at 4(cid:2)C and 3months at after harvest. 2-Ocetenal (E), associated with a nutty, fatty, or
30(cid:2)C, respectively, and also in Cocodrie, prior to, and following grassyflavour,andpentacontonalweredetectedonlyinCocodrie,
storage for 3months at 30(cid:2)C. Most cultivars and storage condi- Dellrose, and Wells. Cocodrie contained the highest number (10)
510 R.J.Bryant,A.M.McClung/FoodChemistry124(2011)501–513
y-
n-Heptadecylcclohexane 4e-15 X F/S/TF/S/TXF/S/T XS/TF/S/T
ne
xa
he
o
ycl
Heptylc 4e-14 XF/S/T XF/S/T XF/S/T X F/S/T
ne
deca
nta
pe
y
4-Acetox 4e-13 X F/S/T XF/S/TF/S/T S
ne
3,5,24-Trimethyltetraconta 4e-12 X F/S/TF/S/TXF/S/TF/S/T XF/S/TF/S/T XF/S/TF/S/TF/S/TX F/S/TXF/S/T FXF/S/T X F/S/T
ne
nta
o
Tritetrac 4e-11 X F/S/T XF/S/TF/S/TF/S/TXF/S/T X F/S/T XF/S/T F/S/T XF/S/TF/S/T
ne
1-Chloro-nonadeca 4e-10 XF/S/T X F/S/T
ne
deca
Hepta 4e-9 X F/S/TF/S/T S/T X F/S/TF/S/T S/TF/S/T F/S/T X F/S/TF/S/TXF/S XF/S/TF/S/T XF/S/TF/S/TF/S/T
ne
deca
Nona 4e-8 X F/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TX F/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TXF/S/TF/S/TF/S/TX F/S/TF/S/TX F/S/T
6-Methyl-octadecane 4e-7 F/T XF/S/TF/S/TF/S/T S/T X F/S/T
5-Ethyl-4-methyl-2-phenyl-1,3-dioxane 4e-6 X F/S/TS/TF/S/T S/TT XF/S/TT TTS/T TT XTF/S/T TTF/TXTF/S/T TF/T
ne
nta
Dotriaco 4e-5 X F/S/T XF/S/T F/S/T XF/TF/S/T X F/S/T F/S/TX F/S/T XF/S/T XF/S/T XF/S/TF/S/T dmonth.
Table4eaAlkanesdetectedinfreshlyharvestedriceandfollowingstorage. Alkanes 1-4-[(1-2-Chloro-Cyclohexyl-Methylethyl)thio]Methyl3-dodecanecyclohexanedecanemethylbutane 4e-14e-24e-34e-4 AromaticXXse230CSF/S/TF/S/T(cid:2)4CF/SF/S/TS/T(cid:2)10CF/S/TF/S/TF/S/T(cid:2)(cid:2)DellmatiXX30CF/S/T(cid:2)4CF/S/TF/S/T(cid:2)10CFF/S/T(cid:2)(cid:2)DellroseXX30CF/S/TS(cid:2)4CS/T(cid:2)10CF/S/TF/S/T(cid:2)(cid:2)IAC60030CS/T(cid:2)4C(cid:2)10CF/S/TF(cid:2)(cid:2)Jasmine8530CF/T(cid:2)4C(cid:2)10C(cid:2)(cid:2)JES30CS/T(cid:2)4C(cid:2)10C(cid:2)(cid:2)SierraX30CSF/S/TS/T(cid:2)4CTS/T(cid:2)10CF/T(cid:2)(cid:2)CocodrieXX30CF/S/TF/S/T(cid:2)4C(cid:2)10CF/S/T(cid:2)(cid:2)WellsXX30CF/TF/S/T(cid:2)4CF/S/T(cid:2)10CF/S/T(cid:2)(cid:2) aX=priortostorage,F=firstmonth,S=secondmonth,andT=thir