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m BULGUR WAFER AND ADJUNCT;

S" FOR FALLOUT SHELTER RATIOI,oC,

A REPORT OF RESEARCH CONDUCTED JULY 1964-JUNE 1965

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PREPARED FOR

,4 OFFICE OF CIVIL DEFENSE

DEPARTMENT OF THE ARMY- OSA

under

Work Order No. OCD-OS-62- r (.,... OCD Work Unit No. '. .

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DTAGRICULTURAL RESEARCH SERVICE

"*" UNITED tIEPARTMENT OF AGRICULTURE

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U, DISTRIBUTION OF THIS DOCUMENT IS UNLIMITED). o5o~oo0

BULGUR WAFER AND ADJUNCTS

FOR FALLOUT SHELTER RATIONS

A report of research conducted July 1964 - June 1965

by

Allan D. Shepherd, Project LeaderRobert E. FerrelRobert J. Horvat

Hawkins NgWilliam G. Lane

UNITED STATES DEPARTMENT OF AGRICULTUREAgricultural Research Service

Western Regional Research Laboratory

Albany, California 94710

Prepared forOffice of Civil DefenseDepartment of Army - OSAContract No. OCD-OS-62-54OCD Work Unit No. 1.311 A

This report has been reviewed in the Office ofCivil Defense and approved for publication.Approval does not signify that the contentsnecessarily reflect the views and policies ofthe Office of Civil Defense.

Distribution of this document is unlimited

/

Acknowledgments

The authors thank the following members of thelaboratory staff: William H. McFadden andDale R. Black for mass spectrographic data;Robert E. Lundin for nuclear magnetic resonancedata; and Roy Thielking, Mrs. Nancy Bellard,and Albert P. Mossman for their technicalassistance.

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TABLE OF CONTENTS

PageSUMMARY . . . ....... . . ....... . . . . . . . v

SECTION 1. DEVELOPMENT OF NEW STABILITY-EVALUATION METHODS . 1A Model System - Methyl Linoleate ......... 1

Volatile components ......... .. 1Non-volatile residual fraction . . . . . 6Oxygen uptake ............... 8Permanent gases .............. 8

Components of Bulgur Vapors . . . . . . 9Acceleration of Rancidity . . . . . .. . 10

SECTION*2. ALTERATIONS IN PROCESSING OF CEREAL INGREDIENT . 12Gun-Puffing . . . . . . . . . . . . . .. 12Hot-Air Puff-Drying ............ 18

Hot-Air Puffing and Textural Measurements. . 21

SECTION 3. ADJUNCTS FOR USE WITH BULGUR WAFERS . . . . . . . 25Cold-Water High-Methoxyl Pectin Jellies . . 25

SECTION 4. STORAGE STABILITY E...L.Y......... 27Bulgur Wafers ....................... 27

Taste-panel evaluation .. .......... . 28Chemical-physical determinations ..... 33

Adjuncts . . . . . . . . .. .... . 33Taste-panel evaluation . . . . . .. 35Chemical-physical determinations . . . . . 35

iii

i

LIST OF TABLES

Pa e1.1 Volatile compourds from autoxidation of

methyl linole;te . . . . . . . . .. . . . . . . . . . 52.1 Some characteristics of soaked hot-air-puffed wheat . . . 202.2 Effect of proce s variables cn product characteristics -

red wheat bulur . . . . . . . . . . . . . 222.3 Effect of proce s variables on product characteristics

white wheat btlgur . ...... .- . • .-. • . . . .234.1 Flavor scores or a 9-point hedonic scale of bulgur wheat

wafers, formulations 1 and 9, stored at -18*F ..... 294.2 Flavor scores of red wheat bulgur wafers, initially and

after 28 months storage ........... . . .. 304.3 Flavor scores of white wheat bulgur wafers, initially

and after 28 months storage ............ . 314.4 Analysis of var ance of flavor scores of wheat wafers. ' 324.5 Changes in oxygen, carbon dioxide, and carbon monoxide

content of heddspace gas after 22 months storage . . . . 344.6 Storage plan for each adjunct under test . . . . . . . .. 364.7 Flavor scores of all adjuncts after 18 months storage. . . 37

LIST OF FIGURES

1.1 Gas chromat~gral of volatile oxidation products ..... 3

1.2 Schematic diagram of capillary chromatograph andp Time-of-Flight! mass spectrometer . . . . . . . . . . . . 4

1.3 Scheme for isolation of components from oxidizedresidual oil i. . .. . . .& . . ..... .* o. . . . . . 7

2.1 Relationship of firing pressure, moisture, and puffindex in gun-puffed bulgur . . . . . . . . . . . . . . . 13

2.2 Relationship of firing pressure, moisture, and puffindex in gun-puffed wheat . . . . . . . . . . . . . . . 14

2.3 Relationship of puff index, moisture, and texture ingun-puffed buligur 15

2.4 Relationship of uff index, re, and texture in' gun-puffed wheat . "• .16

2.5 Relationship of puff index, moisture, and starchsolubilization in gun-puffed wheat ......... . 17

2.6 Relationship of puff index, moisture, and starchsolubilization! in gun-puffed bulgur . . . ... .... 19

iv

BULGUR WAFER AND ADJUNCTS FOR FALLOUT SHELTER RATIONS

SUMMARY

Ini ial development work on the bulgur wheat wafer (the basicfal out shelter ration) and on adjuncts (foods used to modifyor supplement the wafer) was reported in "Food Supply forFallout Shelters" CDM-SR-60-62 Nov. 1962. Continuing andexpanding work on wafer and adjunct dpvelopnent, modification,stozlage, and evaluation was detailed in the annual reports("B Igur Wafers and Adjuncts for Fallout Shelter Rations")for fiscal years 1962, 1963, and 1964. We now report acont!inuation of these efforts.

She f life (stability) may well be the single most importantfactor in determining the ultimate cost of a stockpilingprogram. Development of reliable surveillance testing methodsto measure stability may depend upon an understanding of themechanisms of deterioration. Major emphasis during FY 1965has been in this area. Further elucidation of the productsand mechanism of rancidification have been gained, principallythrough gas liquid chromatography (GLC) and rapid-scan massspectrometry (MS). Thirty-one of the 40 peaks on gas liquidchromatograms of the volatile fraction of an autoxidized modelcompound, methyl linoleate, have been at least tentativelyidentified. They include several hydrocarbons, esters,acetals, alcohols, aldehydes, ketones, and dioxolanes notpreviously reported in the literature. The major componentswere pentenal, hexanal, amyl formate, methyl octonoate, and

substituted dioxolanes. In addition, several complex higher-molecular-weight compounds have been identified by fractiona-tion and GLC plus mass spectral analyses of the non-volatileresidual oils of autoxidized methyl linoleate. Of particularinterest were several alkyl-substituted trioxanes which smellrancid. Several of these compounds may be better indicatorsof in'ipient rancidity than hexanal which has been suggestedbefore.

The consumption of oxygen by autoxidizing methyl linoleate,coupled with the appearance of low-molecular-weight aldehydesin t e volatile fraction, tends to confirm that hydroperoxidesundekgo cleavage to products which in turn oxidize to low-molecular-weight aldehydes. Uptake of oxygen by methyl

linoieate in four weeks was twice the theoretical amountrequired to form the monohydroperoxide.

v

4 7

The early appearance of the permanent gases--carbon monoxide,carbon dioxide, and hydrogen--in the vapors from autoxidizingmethyl linoleate ,and their detection in headspace gases ofbulgur and puffed bulgur stored under oxygen suggest the useof these fixed gases as indicators of incipient rancidity.

- GLC techniques are now being applied to bulgur and puffed.............. bulgurstored-under high oxygen tension-at etevatad temperatures-.

We hope to develop a reliable, accelerated storage stabilitytest. Thus far we have followed the development of hydrocarbonsand carbonyls only. As in the model system, the carbonylconcentrations first increase and then decrease in storage,but the hydrocarbons continue to increase after their firstappearance.

Work has continued on two alternate methods of processing thecereal ingredient: gun puffing and hot-air puff-drying. Gunpuffing of both wheat and bulgur can be manipulated to producewide ranges in the degree of expansion and in the texture ofthe kernels. Gun-puffed b ulgur has a better texture and flavorthan gun-puffed wheat. In hot-air puff-drying, wheat is soakedfor up to 3 days and then puffed in hot air without interveningsteaming. With proper precautions to prevent undesirablemicrobial growth, the product has excellent and somewhatdifferent flavor, high puff indices (2.5-3.0), and good texture.(200-250 m-g torque). Perhaps enzymatic or microbial actLicnduring soaking develops these desirable characteristics.Improvement of both texture and flavor by controlled enzymaticor microbial action appears promising and worth furtherinvestigation.

The final phase of adjunct development was prepar ion of ahigh-methoxyl jelly mix that can be reconstituted Ln coldwater. Comments from two Civil Defense sources w4 re almostcompletely favorable.

Until an objective accelerated test for stability is developedand proven, subjective examination by test panels of productsstored ot normal temperature remains the one sure measure ofshelf life. Such evaluation of both wafers and selectedadjuncts is continuing under a five-year contract with OregonState University. After 28 months' storage of wafers under avariety of conditions, panel results strongly confirmed theprotective action of packaging in nitrogen. The protectiveaction of malt syrup in the recipe is also becoming moresignificant. Chemical tests on the storage samples show

vi

significant changes in nearly all properties being checked.These changes depend to varying degrees on the main storagevariables, especiaily temperature. When the storage testsnear completion, correlations between panel evaluations andthe chemical and physical measurements may uncover a reliableobjective withod for evaluating stability.

Results of panel evaluations after 18 months' storage of thetwelve selected adjuncts indicate a protective action bynitrogen packaging and a secondary protective action bydesiccants. Analysis of headspace gases from samples storedat 100* showed that carbon dioxide develops rapidly if thesamples contain amino acids or peptides. A Maillard-typebrowning reaction may be taking place.

vii

BULGUR WAFER AND ADJUNCTS FOR FALLOUT SHELTER RATIONS

SECTION 1

DEVELOPMENT OF NEW STABILITY-EVALUATION METHODS

In order to establish reliablP objective measurements t at can beapplied in surveillance testing of stored food products, such as thebulgur wafer, it is necessary to understand the chemistry of theirdeterioration and its relation to development of off-flavors oraromas. We stated before that the component in bulgur shelter wafersmost likely to limit their shelf life is the natural wheat lipids.That premise continues to guide our research. No reason for changingit has appeared.

For simplicity much of the work has been performed on a model system,methyl linoleate. Linoleic acid makes up over half of the fattyacids found in wheat lipids and is one of the more unstable. However,we have also done limited work on bulgur in various forms and undervarious conditions of accelerated storage to provide means forevaluating changes in formulation and processing.

A Model System - Methyl Linoleate

Work continued on rigorous identification of the volatile substancesgenerated in autoxidizing methyl linoleate. We used princivallycapillary gas liquid chromatography (GLC) coupled with rapid-scanmass spectrometry (MS), plus preparative GLC, infrared spectroscopy(IR), and nuclear magnetic resonance'(NMR). In addition we beganresearch on identification of some h~gh-boiling components from theresidual oil of oxidized nethyl linoleate by the techniques previouslymentioned, plus some classical chemical procedures.

In preliminary work, electron paramagnetic resonance revealed freeradicals in methyl linoleate under nitrogen atmosphere and at thetemperature of liquid nitrogen and when exposed to ultraviolet light.This work has not been extended during this period because ofdifficulty in preparing suitable model compounds to assist in theinterpretation of the data.

Volatile components

Vapors from the autoxidizing methyl linoleate were collected bypassing oxygen at the rate of 10 ml/min through niethyl linoleate onpurified glass wool, all at room temperature, and passing the exitgases through a U-tube trap at -76'C to condense out the volatiles.The condensate was thetn extracted with 2,2,4-trimethyl pentane, and

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the extract analyzed on a 200-ftz x 0 01-in. capillary column coatedwith General Electric Silicone Oil SF-96 (50). The temperature-programmed chromatogram obtained with a flame ionization detectorcontained 40 fairly prominent and well defined peaks. The chromatogramin Figure 1.1 is typical of several replicate runs.

Minor differences sometimes occurred in the first 4 peaks in replicateruns. For example, propanol (peak 4) was definitely present inmeasurable quantities in the chromatogram from one oxidation experiment,but in a second oxidation it was barely detectable. In anotherinstance, 1-pentane (peak 2) was a substantial peak, whereas in most ,runs it was barely detectable. Beyond peak 4, however, GLC chromato-r,grams from many replicate oxidations lacked significant differences.

For corroborative mass spectral analysis, the effluent end of the GLCcolumn (minus the detector) was connected directly to the vacuummanifold leading to the ion chamber of a Bendix time-of-flight massspectrometer (rapid-scan mass spectrometer) (Figure 1.2). Conditionswere adjusted so that components took the same length of time totravel the column as in normal GLC runs. As each component emergedfrom the column, changes in the mass spectrum were observed on anoscilloscope, and the complete mass spectrum was simultancouslyrecorded on a Minneapolis-Honeywell Visacorder. A mass range of 20-200 mass units was scanned in 1-3 seconds. As with GLC chromatograms,no significant differences in replicate oxidations were observedbeyond peak 4

The compounds identified by these methods appear in Table 1.1. Exceptwhere noted, the mass spectral data were compared with those ofauthentic compounds or with literature data. In addition, mostcompounds were confirmed by comparison of GLC retention times. Thelist includes several hydrocarbons, esters, acetals, alcohols,aldehydes, etones, and dioxolanes not previously reported in theliterature of lipid oxidation. The major components were pentanal,hexanal, amyl formate, methyl octanoate, and substituted dioxolanes.

The oxidizing technique employed. in this study is very mild and probablyrepresents well the conditions in actual storage of the wafer. Themild oxidation may account fcr the large number of compounds which we ..-identified, but which have not been identified by other workers whoused more vigorous oxidi7ing conditions in similar studies. Themildness may also account for the absence of acetaldehyde, heptenal, -

2-octenal, 2-nonenal, 2,4-iVonadienal, and 2,4-decadienal commonlyreported by other workers in the field.

The acetals and dioxoianes in Table 1.1 suggest that some of thesimple carbonyls reported by others, but not found in these studies,may be present in the nonvolatile fraction as higher molecularweight complexes.

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TABLE 1.l.--Volatile compounds from autoxidation of methyl linoleate

Peak8 Mass spec.. Mass spec.No. and GLC confirm. identification alone

1 methyl formate2 i-penteneb3 n-pentane4 propanal*5 n-butanal

7 n-pentana.2pntnn8 no id entifi cat ion

9 isooctane-solvent10 solvent impurity11 n-butanol12 n-hexanal13 n-amyl formate14 2-heptanoneis methyl hexanoate16 n-hexanol17 l,l-dimethoxy-n-hexane18 (2-heptenal)19 (1-octene-3-one)

20no identification21 tI

22 methyl heptanoate23 no identification24252627 methyl octanoate28 no identification29 2-ethyl-4-pentyldioxolane30 isomer of 29

-31- ---- -no- identif ication-32ofi33 2-propyl-4-pentyldioxolane34 isomer of 3335 n-pentyl-n-hexanoate36 1-methoxy-1-n-pentoxy-

n-hexane37 n-butyl-4-pentyldioxolane38 isomer of 3739 2,4-dipentyldioxolane40 isomer of 39

aRefer to chromatogra.. of Fig. 1.1. Some small peaks have notbeen Rumbered.

Suggested'but not confirmed.C Good mass spectral evidence. Retention time off by 15 sec.

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Non-volatile residual fraction

The non-volatile residue from autoxidized methyl linoleate also maycontain degradation products important, in the overall sensory perceptionof deterioration. We have used two approaches to isolate and identifythe decomposition products (Figure 1.3). In both pathways a 4-1/2-ft. x1/4-in. s,ainless-steel preparative GLC column containing 20% Apiezon Mon Chromosorb P was used for the final separation.

Several components were isolated in the extraction procedure. The twomost prominent ones (A & B, Fig. 1.3) have been rigorously identifiedby MS,.IR and NMR.

To confirm the identity of compound A, we synthesized an authenticsample of 8-formyl methyl octanoate by a preparative scheme from theliterature. The IR and mass spectra of the authentic sample of .8-formyl methyl octanoate were identical to those of compound A.Compound B was identified by comparison of its IR and mass spectra withthose of two other members of the same homologous series, 9-formoxymethyl nonanoate and lO-formoxy methyl decanoate, as well as 10-formoxy,ethyl decanoate.

A second fraction of the residue from autoxidized methyl linoleate(peroxide number of approximately 1000) was distilled and concentrated.The final concentrate smelled like rancid food.

We isolated five components from the concentrated distillate, using thepreparative GLC Apiezon column at 1900C. The IR spectra of these fivecompounds were very similar and showed the ether linkage as the onlyfunctional group. The most abundant member of the series (E) washydrolyzed in 2 M aqueous methanolic hydrochloric acid, and theresulting carbonyl compounds were converted into 2,4-dinitrophenyl-hydrazones. Paper chromatography of the hydrazones revealed hexanaland a high-molecular-weight carbonyl compound. A second portion washydrolyzed and the carbonyls isolated from the reaction mixture withether and separated in a 6-ft. GLC column containing 15% Carbowax 20 Mon Chromosorb P. The mass spectra of these two fractions showed theywere hexanal and a C12 unsaturated carbonyl. It seems probable thathexanal was the principle hydrolysis product, and the C19 unsaturatedcarbonyl was an aldol condensation product which formed i rom hexanalduring hydrolysis. Consequently this series of compounds is probablytrioxanes. To confirm this possibility, 2,4,6-tripentyl trioxane wassynthesized from hexanal, purified by preparative GLC, and analyzedby MS. Component E was shown to be 2,4,6-tripentyl trioxane, sinceits MS and IR spectrum were identical with those of the authenticsamples. In further comparisons, 2-butyl-4,6-dipentyl trioxane and2,4-dibutyl-6-pentyl trioxane were synthesized arid shown to be identicalby MS and IR with two other members of the homologous series (C & Drespectively). Work is in progress to isolate enough of the remainingtwo members of the series for MS analysis.

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OXIDIZED RESIDUAL METHYL LINOLEATE

Extract with Isooctane Distill 25*C,I 20!.40,I pressure

Isooctane solution I7 i -

Concentrate,15-20 mm pressure Concentrate,

Concentrated Isooctane I 1solution Concentrated distililate

Preparative GLC Preparative GLCA 1 5X

4 20X 5Xo -,0 0

C D E

172°C 1900C I--- Substituted - - - - - - -trioxanes

*Figure 1.3 Scheme for isolation of components from oxidized residual oil.

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The isolation and identification of these complex higher-molecular-weight compounds from the non-volatile residue further illustrates thecomplexity of fat oxidation and the need for basic studies of puremodel systems such as methyl linoleate. The alkyl-substitutedtrioxanes are particularly interesting because they smell rancid.Their appearance and increase may more closely parallel the develop-ment of sensory rancidity in a stored product than other indicators.This possibility will be explored in continuing work.

-----Oxygen uptake .

The rate of oxygen uptake by methyl linoleate suspended on purifiedglass-wool at room temperature in an atmosphere of oxygen underlaboratory light has been studied to obtain more information aboutthe cause of development of rancidity in the ester. Four-gram samplesof methyl linoleate (97 percent purity) were placed on purified glass-wool in two 10'ml flasks, each fitted with a rubber septum. The flaskswere then connected to a gas burette equipped with a mercury levelingbulb. The gas in the system was replaced with oxygen purified bypassing it through a stainless-steel tube containing copper oxide at3500 and then through tubes containing magnesium perchlorate (anhydrone)and asbestos coated with sodium hydroxide. Analysis of the oxygen bygas chromatography revealed no carbon monoxide, carbon dioxide, orhydrogen. Oxygen uptake was followed over four weeks in one flask;the second was the source for GLC detection of the development ofpermanent gases, as is described below.

The rate of oxygen uptake is an S-shaped curve with time. Uptake isslow during the first seven days, very rapid for the next ten days,and decreases slowly thereaf:er. The methyl linoleate consumed twicethe oxygen theoretically required to form the monohydroperoxide. .Day_(Lillard, D. A. and Day, E. A.. 1964. J. Am. Oil Chemists' Soc. 47:549) has shown that unsaturated aldehydes can be oxidized by oxygenat room temperature to several lower-molecular-weight aldehydes. Suchoxidation may account for the high oxygen uptake and the appearanceof low-molecular-weight aldehydes tn our model system.

-Permanent gases

It is well established that hydroperoxides form during oxidation ofmethyl linoleate,.and various workers have shown that thermal decompo-sition of primary hydroperoxides produces the gases, hydrogen, carbonmonoxide, and carbon dioxide. We suspected that these fixed gaseswould form during the early stages of oxidation of the model system andthat their appearance might be a good test for incipient rancidificationin bulgur and similar products. Analysis for carbon monoxide andcarbon dioxide in headspace vapors over stored products would be muchsimpler and would require less elaborate equipment than would analysisfor hydrocarbon or catbonyl.

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To find fixed gases, vapor samples were withdrawn periodically fromthe second of the two flasks described in the preceding oxygen uptakesection.

Carbon dioxide analysis was on a 16-ft. by 1/4-in. o.d. stainless-steel column containing 33 percent hexamethyl phosphoramide (HMPA) onfirebrick and with a helium exit flow rate of 30 ml. per minute and acolumn temperature of 22*C. Analysis of carbon monoxide was on a12-ft. by 1/8-in. o.d. stainless-steel column containing Linde molecularsieve Type 5A and with a helium exit flow rate of 30 ml. per minuteand a column temperature of 50*C.

Analysis for hydrogen was made on a Fisher Gas Analyzer, Model 25V,equipped with a 6-ft. by 1/8-in. o.d. stainless-steel column containingHMPA on firebrick, followed by a 12-ft. by 1/8-in. o.d. stainless-steelcolumn containing Fisher Type 13A molecular sieve and with an argonexit flow rate of 80 ml. per minute and a column temperature of 22*C.

Carbon monoxide, carbon dioxide, and hydrogen were first detected inthe samples after seven days. At that time the methyl linoleate hadconsumed approximately one-third of the theoretical amount of oxygenrequired to form the ronohydroperoxidcs. We continued to analyzevapor samples from the autoxidizing ester for the next 4 weeks; allfixed gases increased in concentration with time.

In order to eliminate the possibility that the observed fixed gaseswere artifacts, we ran blanks with each GLC analysis. The blankswere prepared by drawing the appropriate volume of oxygen, several-fold larger than that used for permanent gas analysis, from a parallelapparatus containing only purified glass wool and injecting it intothree different GLC chromatographs. Chromatograms from the blanksshowed no peaks with retention times corresponding to those ofauthentic samples of carbon monoxide, carbon dioxide and hydrogen.These gases, perhaps, offer a good possibility for development of arapid, objective test for incipient rancidity of the stored wafersor other fat-containing foods.

Components of Bulgur Vapors

Work has continued with GLC to identify the volatiles from autoxidizingbulgur. We plan now to use the analytical techniques developed forour model system to analyze completely the vapors of rancid bulgur.

Previous work (Bulgur Wafer and Adjuncts for Fallout Shelter Rations,1964) showed the presence of saturated hydrocarbons and carbonyls, andthe present work shows carbon monoxide and carbon dioxide in head-space gases over ground bulgur and puffed ground bulgur.

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The analyses for carbon monoxide, carbon dioxide, and hydrogen were bythe techniques described for permanent gases in the model system.These analyses were carried out on samples of headspace gas overground bulgur and ground puffed bulgur that had been stored underoxygen at 70* and 90*F.for 17 months..

Analyzing for hydrogen in these headspace samples was difficult becausehydrogen, if present, occurs in such minute quantities. GLC chromato-grams from headspace gdses of ground rancidifying bulgur under oxygen

-_ did not consistently show the small peak with a retention timecorresponding to that of hydrogen. The presence of carbon monoxideand carbon dioxide, however, was well established.

Acceleration of Rancidity

Attempts to devise an accelerated storage test t estimate storagestability of bulgur wafers are cortinuing. In ozf model system,methyl linoleate, hydrocarbons emerged before ofi-flavor developedor before the accompanying carbonyl compounds appeared. We are tryingto determine whether the same sequence holds in bulgur and productscontaining bulgur. If hydrocarbons precede off-flavor development inbulgur, they might be an excLedingly sensitive indicator of incipientrancidity.

Freshly prepared ground bulgur and ground hot-air-puffed bulgur weresealed under oxygen in tin cans and stored at 34, 70, 90, and100*F. Controls were samples sealed under nitrogen and stored at thesame temperatures. We took vapor samples (1 to 3 ml) from the cansand analyzed them by GLC for hydrocarbons and carbonyls, principallyhexanal. Shortage of time and equipment precluded analyses forpermanent gases in this series of experiments. After vapor sampling,the materials were checked by sensory methods'for development ofrancid flavor or aroma.

Headspace samples from ground puffed bulgur stored under oxygen at90 and 100F showed an increase in hexanal and pentanal after two

-weeks, but five weeks passed before pentane began to increase. Duringlonger storage at 1000F, hexanal and pentanal decreased, but pentanecontinued to increase. Hexanal and pentanal arose similarly fromground unpuffed bulgur but over longer periods. Under nitrogen,neither product showed any significant changes in the levels ofpentane, hexanal, or pentanal, The taste panel judged none of thesamples rancid through 18 weeks of storage.

To analyze both classes of compounds simultaneously, two parallelpieces of chromatographic equipment were used. The one used forcarbonyls was sensitive to 10 times less material than the one usedfor hydrocarbons. This difference in sensitivity may account for

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the detection of carbonyls before hydrocarbons from the puffed bilguralthough the order was the reverse from the model system. In anycase, the significant observation is that concentration of pentaneincreases with time, whereas the carbonyls reach a peak of concentrationand then decline.

Studies with the model system, methyl linoleate, continue to shellight on the mechanism of oxidative deterioration leading to ranidity.The discovery of substituted dioxolanes, not previously reportedr inthe volatile fraction, provides evidence of an alternative pathway ofoxidation: The 11-hydroperoxide of methyl linoleate could cleave toform a reactive pentyl ketene type of compound which, in turn, cculdreact with the aldehydes formed. We have tentatively establishedthe formation of the llhydroperoxide.

A second series of cyclic ethers, the trialkyl trioxanes appear inthe non-volatile residue of oxidized 4ethyl linoleate. They may~formfrom aldehydes or some free radical a dehyde precursor. The mosicommon of the series, 2,4,6-tripentyl trioxane, is a trimer of hexanal,the principal aldehyde formed in early stages of oxidation.

The consumption of aldehydes in these reactions could e.-plain thediscrepancy between the formation of aldehydes (especially hexanal)and the slow development of rancid taste or aroma.

The work underway with bulgur and puffed bulgur under high oxygentension and high temperature suggests that the lipids in these systemsfollow the same general reactions and pathways as those in the modelsystem. This, of course, needs much c9nfirmation with more extensiveand exhaustive studies.

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SECTION 2

ALTERATIONS IN PROCESSING OF CEREAL INGREDIENT

We are still trying to improve the wheat in the wafer through changesin its texture and flavor. We have considered lowering the cost byusing raw wheat or simplifying the process of expanding the wheatmaterial. A new hot-air puffer, which simulates the commercial pufferat Van Brode Milling Company, has been put into operation and usedto delineate the effects of major operational variables.

Gun Puffing

The study of gun-puffing of wheat ("Bulgur Wafers and Adjuncts forFallout Shelter Rations," 1964) has now been extended to bulgur to . .see if the texture and flavor of gun-puffed bulgur are superiorenough to justify the slightly greater expense.

A single lot of whole-kernel bulgur, commercially prepared from hardred winter wheat by an atmospheric cooking process, was puffed.Portions were adjusted to 10, 13, 16, 19, 22, and 25% moisture, andsamples of each moisture level were fired from the gun at pressuresof 120, 135, 150, 165, and 190 psig. The puffed product was thenevaluated by measuring (a) puff index (bulk density), (b) texture,on the Brabender Hardness Tester, (c) soluble starch, and (d) coloror amount of toasting.

Moisture appears to have a much greater effect on puff index ofbulgur than it does on wheat, as can be seen by comparison ofFigures 2.1 and 2.2. Only at the higher moistures, 19% and above,does firing pressure begin to show a marked effect on bulgur.Whether 22% is in fact the optimum moisture for expansion, asindicated in Figure 2.1, is not entirely clear. The plastic moistpuffed bulgur tends to recompress or deform when it hits the surfacesof the receiving hopper. This deformation is readily visible in the25% moisture samples fired at the higher pressures.

Textural values are related to puff index (Figures 2.3 and 2.4), butbulgur differs from wheat in that there is apparently no moisturedependence as indicated in the wheat. In addition, bulgtir is appreciablymore tender than wheat at all degrees of expansion, except the verylowest (<1.5).

At 16% moisture and below, gun-puffed wheat showed one rate of starchsolubilization over the range of puff index, but the rate increasedas moisture rose from 19% to 25% (Figure 2.5). Perhaps starch at 16%moisture and below is solubilized only by mechanical rupture of thestarch granules, but at 19% and above more cooking (gelatifiizati6n)

-12-

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102.0 3.0 4.0 5.0 6.0

PUFF INDEX

0 Figure 2.3 0 Relationship of puff index, moisture, and texture in gun-puffed bulgur.

-15-

500- GRAIN MOISTURE, %

0= 10 0 =19

X 13 0=22

400-

CQ

200- j

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PUFF INDEX

*_ F igu r e __2 .4 -*_ Relation -ship -of puff -i -n d e ,x, moisture, -and -texture in gun-puffed wheat.

-16-

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PUFF INDEX

* Figure 2.5* Relationship of puff index, moisture,

and starch solubilization in gun-puffed wheat.

-17-

in the gun before explosive decompreszion may solubilize starch bothby hydration and mechanical rupture of the granules. Or mechanicalrupture may increase because of hydration effects. Gun-puffed bulgur,in contrast, shows that the rate of apparent starch solubilizationdecreases constantly as moisture increases (Figure 2.6). .Thissuggests that amylose degrades in bulgur, perhaps hydrolytically,under the conditions of gun puffing or, less probably, the conditionsin the gun strengthen the granule walls with the result thatmechanical rupture on explosive decompression is less.

Color developed in the puffed bulgur about the same as it did inwheat. Overall darkness and redness of the samples increased withfiring pressure. Slightly more toasting was evident in the low-expansion samples, probably because slight dextrinization of starchduring gelatinization allowed additional caramelization or browning.

Gun-puffing offers the advantage over hot-air puffing of providingingredients with expansions greater than 2-fold and consequentlypotentially more tender products. Several breakfast cereal companiesalready have such equipment in regular use.

Hot-Air Puff-Drying

An interesting modification of the hot-air puff-drying method ofpreparing the wheat ingredient was mentioned very briefly in ourprevious report ("Bulgur Wafer and Adjuncts for Fallout ShelterRations," 1964). This technique has been investigated further.

When wheat is soaked in water at room temperature for two to threedays, drained, and then exposed to hot air, it expands, apparentlyfully cooked and with good texture. Microbial action appears afterthe first day, and the final puffed product smells and tastes badif this action is not controlled. Addition of 100-150 ppm availablechlorine (as sodium hypochlorite solution) to the soak watereffectively retards microbial action without noticeably affectingtaste. Concentrations of chlorine above this level adversely affectflavor.

To investigate this process further, we soaked samples of hard redwinter wheat for several time periods at several temperatures. Afterthe soak, the samples were drained, the moisture content of the soakedwheat determined, and the samples puffed in hot air at 500*F with avelocity of 1800-2000 ft/minute. At a wet loading rate of 1 to 1-1/2lb/ft2 , exposure for 70 to 90 seconds produced a lightly toasted, welldried product. Puff indices and hardness (Brabender Hardness Tester)of the puffed product are shown in Table 2.1

-18-

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PUFF INDEX9 Figure 2.6 * Relationship of puff index, moisture,

and starch solubilization in gun-puffed bulgur.

-19-

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Either activity of the natural wheat enzymes or Microbial activity, orboth, probably make thewheat kernel ready for puffing. Temperaturesof 100' and 130*F, which enhance such activities, generally provideproducts with maximum puff indices and minimum hardnesses. The soakedwet wheat which yielded puffed products with low hardness and highpuff indices had a soft endosperm with consistency like toothpaste.

Soaked and hot-air puff-dried wheat resembles puffed bulgur in manyways and might be substituted for bulgur in wafers and other products.The fiber content of the product from whole wheat would be higher thanin puffed bulgur. However, the fiber seems less noticeable and maynot impair its usefulhess.. We produced a product lower in fiber, byfirst partially debranning the wheat in a pearler. Several degrees ofdebranning were tried. We found that the amount of debranning must belimited, perhaps to a level similar to that used for bulgur. Greaterdebranning exposed the endosperm in places; some kernels lost theirshape during soaking; and stuck together during puff-drying.

The opportunity to modify both flavor and texture of expanded productsby controlled enzymatic or microbiological action appears very promising.

Hot-Air Puffing and Textural Measurement

A new pilot model of the continuous hot-air puffer manufactured by theSurface Combustion Company has been installed. Puffing can be variedover a much broader range with this unit than was possible with thesmall unit formerly in use at this Laboratory. An investigation ofthe effect of altering these variables has been conducted. Theparameters checked in the puffer were temperature (450, 500, and 550*F),air vol~city (950, 1650, and 2200 fpm nominal), bed loading (1/2, l, and2 lb/ft ) and residence time (15, 25, and 35 seconds). Two single lotsof bulgur, one a red wheat bulgur from Farmers Cooperative Commission Co.and the other a white wheat bulgur from Armeno Cereal Co., were compared.Although results varied somewhat for the two lots (Tables 2.2 and 2.3)several generalizationscan be drawn. The lowest air velocity (950 fpm)is inadequate to fluidize the grain bed except at 1/2 lb/ft loading.Puff index generally increases with increasing air temperature andvelocity, but control of maximum puffing without overtoasting becomesmore difficult at the more severe conditions. Increasing residence timealso brings about slight increases in puff index, but sometimes leads toovertoasting.

Textural values as measured on the Brabender Hardness Tester showconsistent trends within each series of samples. Texture appears tobe primarily a function of puff index; samples become more tender aspuff index increases. There is evidence in both series, however, thatincreased residence time in the puffer, beyond that necessary forachieving maximum puff index, does make the product slightly more tender.

-21-

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This information will enable us to operate the Surface CombustionPuffer to obtain optimum condition for puffing, texture, and toastingon a variety of bulgurs made by different processes and to determinedifferences brought about by changes in processing.

One aspect of textural measurement, not presently understood, showsup in these two series. At comparable puff index, the puffed whitebulgur samples consistently have textural values approximately 100 M-gmhigher than the puffed red bulgurs. In other samples, differences of

___. thismagnitudeare usually easy to detect inbite tests.__Detectionwas difficult with these samples. This discrepancy has been notedbefore.

The hardness tester is essentially a burr mill connected to adynamometer to measure the force required to grind the sample. Spacingbetween the burr is- adjustable. Standard operation is with the burrsclose together so that the puffed bulgur is first broken into smallparticles in the top of the equipment, then it goes between the burrswhere the main grinding force is exerted. We are thus measuring thehardness mainly of the endosperm portion of the sample and perhaps notthe total bite characteristics. To test the effect of changing theburr settings, a series of 5 puffed bulgurs were ground with burr.settings from very fine to very coarse. The results were checkedagainst subjective evaluations by a panel of 15 members. The presentstandard technique with the fine setting gave values that agreed bestwith panel judgments and gave the greatest spread of values (i.e.,the greatest sensitivity).

While newer and more comprehensive methods of textural measurementsneed to be investigated, the standard technique currently in useappears sufficiently valid for present purposes.

-24-

SECTION 3

ADJUNCTS FOR USE WITH THE BULGUR WAFER

Adjuncts are a series of food items for use in small quantity with

the basic shelter ration, the bulgur-type wheat wafer, only to provide

variety and thereby relieve the monotony of a single-item diet.

The adjuncts are not designed to provide particular nutrients, nor

do they in any way attempt to alter the nutritional balance originally

set for the ration.

We have formulated a number of dry mixes which can be prepared by

addition of water and, in some cases, by heating to provide soups,

sauces, gravies, spreads, toppings, etc. The development work on

adjuncts has been substantially completed and reported in the annual

reports for Fiscal Years 1962, 1963, and 1964. Some final developmental

work is reported here on a one-package, cold-water, high-methoxyl

pectin jelly and its evaluation in two Office of Civil Defense Shelter

Experience Tests.

Cold-Water High-Methoxyl Pectin Jellies

The jellying ingredient for this product is prepared by drum drying

a mixture of high-methoxyl pectin (Sunkist Growers 03430) and sugar

dissolved in water at about 20-25% solids. The sugar/pectin ratio

and pH of the jellying ingredient were varied, to observe the influence

of this variation on the final jelly. A jellying agredient with

15/1 sugar/pectin ratio adjusted to pH 6 was seleted as best.

The basic recipe for the cold water, high-methoxyl, pectin jelly is:

7 by

Drum-dried sugar pectin mix 11.1

(15:1 sugar/pectin, p 6)

Sugar, granulated 87.1

Delta glucono lactone 1.8

Artificial flavorings and colors may be added in the quantities shown

in Formulas for Adjuncts numbers 66 through 74 (Appendix, Report forFY 1964), to provide a variety of flavors.

Twelve cans of a dry mix of the cold-water jelly were prepared intwo flavors, strawberry and raspberry, and furnished to Mr. George W.

Wassmer, Staff Director, Material Technical Division, Material Office,

-25-

Office of Civil Defense, for trial in a shelter exercise in a ShelterManagement Instructor Course at three locations throughout the country.

Th .is contained a plastic bag with pre-formed spout and a paper-coy. ced wire tape to serve in preparing and dispensing the jelly. Thefollowing instructions were provided on the label of each can:

Cut top from can and remove plasticbag. Pour powder into bag by slippingtop of bag over top of can and inverting.Fill can with water to mark on inside ofcan and pour water over powder. (Savecan.) Close bag by twisting it about4 inches above the mixture, and tiesecurely with'wire tape; do not trap too

-much air. Mix contents by tipping thebag back and forth and kneading thecontents for about 3 minutes. Place thejelly, bag and all, in the can and allowto stand until gelled (about 3 hours).To serve, cut off spout at bottom of bagand squeeze bag to extrude jelly.

Reports from two of the three Civil-Defense courses where the jellywas used have been received. The comments were almost completelyfavorable. Users felt the jellies improved palatability of the ration.,There were other comments such as raspberry flavor was more acceptable,strawberry too sweet, the jelly made them thirsty, and gel time shouldbe shorter.

The gel time can be shortened only at the expense of a poorer texture.Three hours setting time appears practical since it allows a jelly tobe prepared after one meal to be ready for the next. The jelly maybe held satisfactorily for several hours; very little change in gelstrength occurs in three hours.

One cogent comment on preparation was that the can opener issued in.shelter supplies left jagged edges that might tear the mixing bagsand possibly injure fingers. A change in instructions may be required.The plastic bag need not be placed in the can after mixing as calledfor in the instructions; this was merely a convenience. The bag maybe placed on a table top just as well. The jagged edges should notinterfere seriously with the removal of the plastic bag, pouring outof the can contents, measuring and pouring the water.

These tests provided other important information. First, thepreparation of the jelly for serving was easy for users unfamiliarwith the product. Second, it was prepared successfully with twodifferent water supplies.

-26-

SECTION 4

STORAGE STABILITY

Storage stability of foods for stockpiling in shelters may well bethe dominant factor in their true cost. In spite of our efforts, aswell as those of many other workers in the field, to develop reliable,quick, objective measurement of shelf life, the one sure test remainslong-term storage of the material at normal temperatures and periodicevaluation of various quality factors by subjective taste panel methods.

Contractural arrangements were made on June 29, 1962, with Oregon StateUniversity to conduct a five-year study of storage stability of thebulgur shelter wafer, and a similar study of 12 selected adjuncts wasstarted one year later. Results emerging from these contract studiesare discussed below.

Bulgur Wafers

The contract on waferstability provides for taste panel evaluationof 16 types of bulgur wafers stored at three temperaturts (40, 70,and 100*F). Several physical-chemical tests are also performed, todiscover any correlations between changes in physical-chemicalcharacteristics and panel evaluation. Such correlations, if they arefound, might lead to quick, reliable, objective methods for surveillancetesting of stockpiled wafers. The wafers are sampled at 6-monthintervals.

Red and white wheats with appropriate protein content were providedby the Fisher Flouring Mills Co., Seattle, Washington. They processedpart of each lot into bulgur by a pressure-cooking process. Theremainder was processed into bulgur by atmospheric cooking at theArmeno Cereal Co., Westboro, Massachusetts. All bulgur was puffedby the Van Brode Milling Co., Inc., Clinton, Massachusetts, and madeinto wafers incorporating the following treatments:

Red Wheat White Wheat

1 Pressure cooked, malt binder, nitrogen pack (REFERENCE) 9

2 Pressure cooked, 'malt binder, air pack 10

3 Pressure cooked, corn sirup binder, nitrogen pack 11

4 Pressure cooked, corn sirup binder, air pack 12

-27-

5 Cooked in atmosphere, malt binder, nitrogen pack 13

6 Cooked in atmosphere, malt binder, air pack 14

7 Cooked in atmosphere, corn slrup binder, nitrogen pack 15

8 Cooked in atmosphere, corn sirup binder, air pack 16

Taste-panel evaluaton

One red-wheat and one white-wheat formulation, arbitrarily chosen,serve as reference samples and also serve as controls held at -18°F.The flavor of control samples is scored at each sampling period bymeans of a 9-point hedonic scale ranging from 1 for the lowest to 9for the highest rating. Results of these judgments through 28 monthsof storage are given in Table 4.1. At any given sampling time, no

... .. significant difference was found between red wheat and white wheatwafers. No statement of significance is possible for the zero-timesamples because they were not judged by the same panel. The variationin flavor scores as. the test progresses appears to be only a variationin taste panel performance.

At each sampling period the reference formulations (numbers 1 and 9)

stored at 40, 70, and 100*F are compared with their appropriatecontrols (stored at -18*) by means of a reference-preference test ona 9-point hedonic scale. Each of the other formulations is thencompared with its appropriate reference sample by means of the samereference-preference test. Tables 4.2 and 4.3 compare mean scoresof the 28-month samples with the original mean scores.

The analysis of variance for the 28-month storage data, within thethree temperature groups and considering red wheat and white wheatseparately, is shown in Table 4.4.

The protective effect of nitrogen packing on flavor becomes morepronounced as' the storage test cbntinues. The estimate of the economicvalue of inert gas pack previously reported (see Report "Bulgur Wafersand Adjuncts for Fallout Shelter Rations," 1964, p. 2) appears to be

. - becoming more valid. Data in Tables 4.2 and 4.3 indicate that shelf.-life can be extended considerably by nitrogen packaging, particularlywhen associated with the protection imparted by malt sirup.

Whether malt sirup stabilizes the wafer by masking the rancid' flavoror because it contains some particularly effective antioxidant is notclear. Its stabilizing effect, however, is becoming more pronouncedas these storage tests continue. Its slight additional cost over cornsirup, one-third of a cent per pound of wafer, may well be justified.

-28-

. ... . .. -- -"... ... . ... " - / 7 : ' ' ' ' -' .....

Table 4.1

Flavor scores on a 9-point hedonic scaleA /of bulgur wheat

wafers, formulations 1 and 9, stored at -18°F

Storage time, months

b/ 4. 10 16 22 28

Red wheat 6.40 6.03 5.68 6.53 6.26 6.22

White wheat 5.72 6.41 5.82 6.42 6.20 6.39

I is lowest, 9 highest.

b/,At 0 time, red wheat and white wheat samples were judged bydifferent panels and, therefore, cannot be compared.

-29-

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Significant differences between the two cooking processes are beginningto appear. The panel showed a significant preference for atmospheric-processed bulgur over the samples made from pressure-processed bulgur.Since atmospheric-processed bulgur expands less during puffing thanthat processed under pressure, the stability difference may be due tothe less porous structure in the atmospheric-processed material. Orit may be due to incipient degradation brought about by the higherprocess temperatureq under pressure. Whatever the cause, we need toknow more about the changes occurring in wheat during processing.

ChemLcal-physical determinations

At each sampling period, each lot of wafers is analyzed to determinepercentage fato peroxide number, thiobarbituric acid number, carbonyls,and diene values. Gas chromatograms (aromagrams) are also prepared.The contract was extended to include analysis of headspace gas forcarbon dioxide, carbon monoxide, oxygen, and pentane.

Analyses have been completed on samples drawn from storage after 22months. Changes are occurring in iearly all factors. being studied.The changes are influenced to a varying degree by all the variablesof interest except type of wheat. Temperature exerts the mostconsistent influence. Of particular interest are the changes in theso-called permanent gases or headspace gases (Table 4.5). Notethat carbon monoxide has appeared only in the air-packed samples. Itsappearance generall, parallels the disappearance of oxygen. Carbondioxide has appeared in all packs but generally to a greater extentin the air pack. The changes in these permanent gases in the headspacefollow the same pattern as was reported in section I from the studieson the model system. Pentane, however, has not been observed in anyof the wafer samples.

Analytical data are steadily accumulating. When sufficient changes

in all chemical-physical factors and taste panel evaluations havetaken place, correlations between the several chemical-physicalvalues and panel results will be made. It is on the basis of thesecorrelations that the value of any single analysis for predictingstorage stability may be determined.

Adjuncts

The contract to determine the stability of adjuncts in normal storageprovides for taste panel evaluation of twelve representative adjuncts:apple topping, beef soup, butterscotch topping, chili sauce, chbcolatepudding, cream of chicken soup, curry sauce, Oriental sauce, paprikagravy, raspberry jelly, strawberry spread, wild cherry icing. Samplesstored at 40, 70, and 100*F are to be compared with nitrogen-packedcontrols at -18*F. All sample adjuncts are packed in tin cans, with

-33-

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nitrogen atmosphere in half the samples and air in the other half.Five adjuncts low in moisture are packed without desiccants; the otherseven higher in moisture are packed with and without in-packagedesiccant. Table 4.6 lists the package and storage treatment givenall 12 adjuncts. They are sampled at 6-month intervals over aperiod of 5 years.

Taste-panel evaluation

At the beginning of the storage study and at each test period allsamples were evaluated before, during, and after preparation, by anexpert panel of four judges. Odor, texture, color, and ease ofpreparation are scored on a 6-point hedonic scale (0-normal to5-extremely off). The prepared adjuncts were evaluated each timefor flavor by a large taste panel using a 9-point hedonic scale.

After 18 months' storage the expert panel gave only slightly alteredscores on preparation. In most casE.s the difference lay in the colorof the dry mix or the rehydrated mix or both stored at the highertemperatures. Only the cream of chicken soup mix exhibited a changeof any real consequence; the color score went from 0 to .3 at all threesteps in preparation for the two samples stored at 100*F. Some samplesexhibited slight changes of texture of the rehydrated sample, but onlyone, the Oriental sauce, showed a major change: it became too thickfor convenient dispensing.

Large-panel evaluations of flavor have been completed on all samplesafter 18 months' storage. Mean flavor scores are given in Table 4.7.

The protective actionof nitrogen packaging is shown particularly bythe flavor scores on apple topping, Oriental sauce, and paprika gravy.All adjuncts, except beef soup, that contain desiccant scored higher,attesting to the protective effect of low moisture. The effects ofhigh temperature are especially demonstrated by the lower flavor scoresgiven apple topping, butterscotch topping, chicken soup, and Orientalsauce stored at 100*F. As storage continues, these trends willprobably become more pronounced and the true value of the protectivepacking can be established.

Chemical-physical determinations

On the samples possessing flow characteristics, Bostwick Consistometerreadings are made in order to have objective measurement of changesin consistency during storage. Samples in which consistency was notedas altered by the panel of expert judges were also observed to bechanging in Consistometer readings. The Oriental sauce, which receiveda subjective score of 3 at the end of 12 months, was too thick togive a Consistometer reading.

-35-

Table 4.6

Storage plan for each adjunct under test

Code number Treatment Can code

Ia/ -18*F, nitrogen, desiccant 1-N-D(for products packed with desiccant)

Ia/ -18*F, nitrogen 1-N(for products packed without desiccant)

2b 40*F, nitrogen 2-N

-70*F, nitrogen |__ 3-N

4b- 100F, nitro~enI 4-N

5b/ 40*F, oxygen 2-0

6/ 70*F, oxygen 3-0

71 100F, oxygen 440

8 40F, nitrogen, desiccant 2-N-D

9 70F, nitrogen, desiccant 3-N-D

10 100*F, nitrogen, desiccant # 4-N-D

11 40*F, oxygen, desiccant 2-0-D

12 70*F, oxygen, desiccant 3-0-D

13 100*F, oxygen, desiccant 4-0-D

-a/Control samples.

b/Five low-moisture adjuncts: apple topping, butterscotch topping,

raspberry jelly, strawberry spread, and wild cherry icing, packed onlywithout desiccant and subject to only this portion of test.

-36-

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-37-

The headspace gas of all samples is analyzed for carbon dioxide, andfhe nitrogen-packed samples for oxygen. If appreciable oxygen isdetected in nitrogen-packs, the samples are rejected and new onesdrawn. Carbon dioxide is considered an objective measure of degradation.

Carbon dioxide first appeared in headspace gas of a few samples afterthey had been stored for six months at high temperaturer. In fact,.both samples of beef soup stored at OOeF were hard-swells with veryhigh carbon dioxide content at 6 months; they had to be removed fromthe test. Carbon dioxide has continued to increase in all samplesstored at 100* with no desiccant, up to the 18month check.Afpackdsamples developed consistently more carbon dibxide than did nitrogenpacks. No samples packed with desiccant have shown any significantquantity of carbon dioxide up'to 18 months.

Examination of the components of the various adjuncts suggests that ........a Maillard-type browning reaction may be responsible for thedevelopment of carbon dioxide, since only the adjuncts containing noamino acids, peptides, or proteins are still free of this compound inthe headspace gas.

Correlation of the results of these objective tests with thesubjective results from panel evaluations will be made when enoughdata have accumulated. The value of these tests for surveillancesampling will rest on these correlations.

Reference to a company or product name does not imply approval orrecomnmendation of the product by the U. S. Department ofAgriculture to the exclusion of others that may be suitable.

-38-

-e- . -

UNCLASSIFIEDSecurity Clasuification

AnUal r.eportmn fo peri1culye 1964 rc toe30 viu e 1965.sfie

Seperd Atllzatn R&D Ferrel, Rober E.;ana Sovt, Roer J Nawin; n

1lan, Ci ia . 71

5. acotirtA ORTE rnO 5.. reporAto~ andoR inetwiUR(S)

Anua ~ sr epor 1300 Noid1Juy16 t 0J ne195

S. ATaOs Not . 310 name OAE RPRTN() Ap.euwJee amybeed

Lae WorklUitm G.1Nn

I. REPORSLTY/ATEO NOTITLCOES A49 76 o i Rr

00. Dsriuto ofTRC thi document N.Il isnimitred.".parmuac

aI. TskPPMNTA. 1310S 9. OT4 Ohs R MITAYo~ru~f ACTIVITY0401i

Office of Civil DefenseOffice of the Secretary d the Army

____________________________ Washington, D. C. 20310IS. AVITRACT

Vapors from rancidifying bulgur and from autoxidized methyl linoleate, a modelcompound, are being analyzed and identified by gas liquid chromatography andmass spectrometry. Thirty-one compounds have now been tentatively identifiedin studies on the model sy-tem. The presence of some of these compounds invapors from rancid bulgur has been verified. We have made further study ofgun-puffing and hot-air puff-drying as alternate means of preparing wheatingredients for the wafer. Development of a jelly that sets with cold wateressentially concludes development work on adjuncts.

Long-term (five-year) storage studies of bulgur waferm and adjuncts arecontinuing. Taste panel evaluations to date indicate that shelf life ofboth types of products can be extended with nitrogen-packaging. The use ofmalt instead of corn syrup in wafer formulation and of in-package desiccantswith adjuncts also extends shelf life. Chemical-physical measurements ofchanges taking place are being made on duplicates of the samples evaluatedby the taste panel to find a test that will correlate wi 'th organolepticevaluations, but as yet no meaningful correlations have been found.

D D IFJomS 1473 UNCLASSIFIEDSecudty Classification

Unclassi fledSecuritV Cldisificatzon

t4 LINK A LINK S LINK C

PaLn WY ,oLa R7 nOLE ,T

FoodWheatBulgur WafersStorage StabilityFallout SheltersSauces and SpreadsMethyl LinoleateAutoxidationTaste Panel

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o-.