CA1059822A - Phosphate/lemon juice anti-oxidant composition and method - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Anhydrous sodium tripolyphosphate is hydrated with a solution of lemon juice, forming a dry granular mixture capable of long periods of storage with little or no reduction in anti-oxidant activity of the lemon juice or any of the desirable properties of the tripolyphosphate.
Erythorbates or ascorbates may be used with the tripoly-phosphate lemon juice mixture.

Description

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. The instant invention relates to new and use~ul meat treating compositions. M~re particularly, the in-stant invention relates to meat treating compositions in ` dry, free-flowing, homogeneous powder form comprising sod~
.. ium tripolyphosphate hexahydrate in which the water of hy- .
: ' dration contains lemon juice solid~; to methods of prepar- ;
ing such compositions; and to methods o~ employing such compositions in the treatntent of meat to maintain the color, ~ taste and fresh quality thereof throughout prolonged cold :;~
;~ ~ . and frozen storage and throughout the cooking process.
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i~ Sodium tripolyphosphate is known to be a safe - ~`
; 20 additive for foods ~see EIall, United States Patent No.

2,513,904, "Curing of Meat to Inhibit Undesirable Color Change"). I$ has bsen used to co~trol oxidative chang~s - . :

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: ' , ~ `. ' ~, , ~a1598~6"2 in foods (see the article by M. WO Zipser and B. M. Watts, 1961. "Oxidative Rancidity in Cooked ~ullet", Food Tech-, 15, 318). The anti-oxidant activity of sodium tripolyphosphate, however, is not effective for many types of foods. For example, sodium tripolyphosphate has very little effect on the oxidative instability of raw fatty fish. With respect to salmon, sodium tripolyphosphate has little or no effect on the oxidative changes in raw salmon flesh.

:-Small amounts of polyphosphates, including sodium tripolyphosphate, have baen combined with a mixture of tetra-sodium pyrophosphate, tetrapotassium pyrophosphate and di-sodium phosphate together with an acidulent such as citric . .. .
acid, tartaric acid or other suikable food acid and employed in the curing of meats ~see United States Patent No. 2,876, : , 115, Epstein, '`Meat Processing and Composition'Therefor").

Such compositions are said to aid in the so~tening of the :
cell membranes of meats allowing for ~etter utilization o~

;cell contents such as albumen and hemoglobin.
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20Sodium tripolyphosphate also has been employed as a component in compositions designed to preserve the red s color of packaged meats (see United States Patent NoO 3,154, 423, Voegeli et al., "Compo~sition for Treating Meat Prior to Packaging") The patentee employs a synergistic four com~-ponent mixture comprising a poising agent to control oxida-tion-reduction potential, such as sodium and potassium salts of ascorbic acid, erythorbic acid and reductic acid; a se-questering agent to complex polyvalent metal ions, such as sodium and potassium salts of citxic acid and tartaric acidi a food grade inhibitor of the removal of oxygen from air .

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DS~322 through bacterial actlvity, such as sodium and potassium salts of parahydroxybenzoic acid and sodium benzoate; a phospllate buffering agent which also may serve as a se-questerant such as sodium tripolyphosphate. In the work-inq examples of the patent, meat products treated inaccordance with the invention are described which contain 2,000 ppm added phosphate and 1,000 ppm each of added citric acid, ascorbic acid and benzoate.

Anhydrous sodium tripolyphosphate has been hydrated by various processes in the prior art to produce intimately . .. .
admixed food additive compositions. In United States Patent No. 3,401,046, Mahon, "Method of Makiny a Composition Useful in Meat Curing", a hvdrate of tripolyphosphate and sodium nitrite or nitrate is used ~n meat curing.
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Lemon Juice which has a relatively high content of ascorbic acid and other natura:L anti-oxidants together with significant quantities of citric acid, has been k~own to exert an effective anti-oxidant stability and flavor im-parting action in various foods such as fruits, vegetables a~d meat products ~ee, for example, United States Patent No. 2,788,281, Guadagni, "Increasing the Flavor and Otller Quantities of Foods", and Vnited States Patent No. 3,113, 030, Brody, "Method of Preparing a Liquid Meat Product").
Lemon Juice, however, has not achieved commercial importance in a number of potential applications because it is sus-ceptable to attack by bacteria and, therefore, must be vacuum packayed or refrigerated, and being largely composed of water even in concentxated forms, it is relatively expen-sive to ship and to store. ~emon Juice has been prepared in powdered form, but it has not become commercially available ~5~
as an anti-oxidant in this form eikher, partly because of the ~ossibility of the loss of anti-oxidant activity ~' during th~ dehydration process (note V.S. Pat~nt No.

3,298,838, Villarreal, "Process for Preparing Soluble Citrus Fruit Powder", on the loss of ascorbic acid during dehydration of citrus fruit juice), and partly becausa the dehydration process is relatively expensive. In addition, large portions of inext ingredients such as dextrose are required to enhance the drying and storage properties~ ;
~.

' 10 ' Ascorbic acid, its isomer erythorbic acid, and their sodium salts also are known to be safe and beneficial additives for foods. Although they have been used with ~' sodium tripolyphosphate in admixture, they have never been `~ ;
used, so far as applicant i5 aware, with a sodium tripoly~
;' 15 phosphate-lemon juice hydrate as contemplated by the in-;' ' stant invention. '' ., ~.

As pointed out above, the instant invention, in its composition aspect, may be described as residing in the concept of a new and useful meat treating composit~on in dry, free-flowing, homogeneous powder form comprising sod-ium tripolyphosphate hexahydrate in which the water of hy-dation contains lemon juiae solids. It is comtemp'lated '~
that effective quantities of such hydrate will be employed in the treatment of meat, including poultry, red meat and ~;~
25 ' fish, in order to maintain the color, taste and fresh qual- ' ity of the meat througllout prolonged cold and frozen stor- ~' age and throughout the thawing and cooking process~

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~ 0 5~ 8A~2 The instant invention is based upon applicant's discovery that the sodium tripolyphosphate-lemon juice composition described above is useful not only for main-taining the color, taste and fresh quality of meat but affords many advantages not heretofore possible in known meat treating compositions. By use of the hydration tech-nique, applicant has been able to combine sodium tri-polyphosphate with a natural liquid product, lemon juice,.
so as to obtain a new single composition. The sodium tri-polyphosphate-lemon juice composition of this invention is a completely homogeneous, dry, free-flowing powder in . which the components are physically inseparable. The com-position, therefore, will be of uniform composition through-- out each package. The uneven distribution and non-uniform treatment which would be expected from a mixture of small quantities of lemon juice solids and sodium tripolyphos- -~
phate has been eliminated. Hydration wit11 the natural mois-- ture in lemon juice, or lemon juice concentrate, locks in a . ~
uniform composition and is economical. Further, the expense . . : . .
and difficulty of handling the naturàl liquid product, and/or ~-the expense and difficulty of xeducing the natural liquid . . .
product to-a dry concentrate, has been eliminated while re-taining in the hydrate the benefit of each of the individual components. Appl-icant has found also that the claimed com-positions are effective in maintaining the color, taste andfresh qualities of meat even though the quantity of ascorbic acid and citric acid added to the meat in this form is far smaller than would have been expscted from the teachinys of the prior art to exert effective anti-oxidant action, and the need for added benzoate is totally eliminated. Further, - applicant has found that, used with sodium erythorbate or . - ' ' .

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ascorbate, the compositions of this invention are effective even to achieve oxidative stability in such foods as fresh pork sausage.

The sodium tripolyphosphate-lemon juice hydrate composition of this invention may be prepared by hydrating ', sodium tripolyphosphate with the lemon juice, preferably -in concentrated ~orm. The hydration step is performed in such a way and in such proportion of sodium tripolyphosphate ~
to lemon juice that the resulting product is a dry, free- ,~ ;
flowing powder. The preparation of the lemon juice tripoly-phosphate composition should be performed bearing in mind that tripolyphosphate forms a hexahydrate.` Although more ~' ,.
than six moles of water for each mole of tripolyphosphate ' may be present, since part of the water may be evaporated , 15 during the hydration process because of the heat of hydra-tion, it is recommended that not more than'about six moles ' of water be present during the hydration process for each ~-; ~ mole of anhydrous sodium tripolyphosphate. Ordinary lemon ' ~ juice contains-fxom about 90 to about 94 percent water. ~'~
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~ 20 Commercial concentrated lemon juice will normally contain , , about 40 to about 65 percent water. For the hydration of ',~

:; sodium tripolyphosphate, it is preferred to use lemon juice ' .:; ` :
containing about 63 percent water which has been diluted ~'' by the addition of at least half again as much water, up to ~', '~ -- 25 an equal amount. Thus, the final lemon juice with whic,h ;~,~' '-'the sodium tripolyphosphate is hydrated and which is in-cluded in the term,"lemon Juice", preferably will contain , from about 17 percent to about 38 percent lemon juice solids, `, - and the balance water. `'' :' ' , ~`

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However, any dry hydrate composition comprising sodi~m tri-polyphosphate and lemon juice solids in a weight ratio of from about 7:1 to 70:1 may be usedO I~ydrates of this in-vention having such composition are added to the meat to be treated by any of the techniques conventional ln the art.
Effective results are obtain~d usually by employing the hy-drate in quantities ranging from about 0.2 to abou~ 0.6 per-cent by weight of the meat.

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An indication of the anti-oxidan~ activity of lemon juice is obtained by using an assay for ascorbata in which the reduction o~ a dye, 2,6-dichlorophenolindophenol, is ob-served according to the procedure in M. B. Jacobsj Chemical Ana~y~is of Fooa and Food Products, D. Van Nostrand Co., Princeton, New Jersey, 727 (1958~. By this method, the aver-I 15 age concentration of ascorbate in lemon juice is approximately ., - 400 parts per million. The concentration of citric acid in lemon juice is about 60,000 parts per million.
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The best mode contemplated by applicant for carry-ing out his invention is illustrated in the following work~

ing examples; no limitation being intended except as set forth in the appended claims.
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Thirt~ milliliters of natural strength Borden REALEMON~lemon juice (about 90 to about 94 percent water) were gradually mixed with 100 grams of anhydrous sodium tripolyphosphate. The resulting powder was then assayed -~ for ascorbate content. The lenon juice sodium tripoly- ~

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phosphate composition assayed 112.~ ppm of active ascorbate.
The weight ratio of sodium tripolyphosphate to lemon juice solids exclusive of water of h~dration i5 in the range of about 33.3:1 to about 56~

.. ' . ~ ~;' .; ' , In this preparation, Sunkist~concentrated lemon . juice was added to anhydrous sodium tripolyphosphate in the . amounts indicated with the results shown in Table 1.

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n~ rl ,C ~ ~ -rl ~ ~) ~J r l u~
h`~ ~ ~ a) O V rd . ~ O O O
~ J a) rl (~ r~ O O ~ u~ ~ \ O
;~ v ~1 o _ ~ u ~' a) ~ ~J ~1~ .IJ ~) ~rl V
O ~rl ~ ,C ~ rl~ * V (~ ~ C i~ rl v ~:1 o 1~ ~ :~ ~n . ~t Q u~ Q aJ h r-r. u~ ~ ~ F. 1 1 0 ~ 4 ~ ~ tl~ ~ E ~
a) o r-l C ~ O P~U O 1l1 0 ~1 ~ ~; ,C
r~ o C u~ O ~D U F~ ~ o V C? O , C ~ ~ r O ~ ~ O O ~ ~ u~ ~ ~) ~ ~rl u~ O
1 S-l O ~ O ~ ~ (d Q~ ~rl ~ O Ei r-l O h h a) V O O ~ ~ a) O ,C C) ~3 r l t~ ~) ~1~1 ~ ~ u~ ~ r-l .
1 30 23.1 337.93970 1270 Hard, 7.6:1 -sticky . powder 2 25 20.0 29 ~ Hard, 9.1:1 sticky powder ~ .

; 3 20 16.7 30 -- -- -- Hard, 11.4:1 - sticky - - powder . ,~ .
`; 4 15 1300 26 -- ~~ Hard, , 15.1:1 . sticky . powder ' I ' ' `~ ."
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Increase.in temperature du~ to : the reaction. ~ .

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Two rather small batches o~ lemon/juice tripoly-phosphate concentrations were prepared according to a formula ;~
- in which.15 and.20 milliliters of concentrated lemon.juice . and lS and 10 milliliters of water were added respectively to .
; . . 100 grams of anhydrous sodium tripolyphosphate. The results ..
are shown in Table 2. The tendency of the composition to cake .
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was tested hy adding the composition to water and allowing it ~;
:; to stand, then attempting to disperse. A passing result is . achieved if the composition is dispersed within one and one-half minutes.
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'~ - ' ' ' ' : '-, TABLE II
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R.~ ~ r-i O ~ a) o .Y O ,C: O
" ."J~ ~ C) '. . . .; ' 1 15 1511.7 . 55 Passed Free-flowing 18 : . . . . powder .2.. 20 10 15.4 48 Passed Free-~.lowing 13.5 : powder ~:.; . . :
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Examples 4 and 5 illustrate the preparation of , -.:, other composi.tions.

:-EXAMPLE 4 :.' . Foùr hundred fifty-four grams~concentrated lemon .' 10 juice (containing 63.percent water) and 227 milliliters water , were added to 2,270 grams of food grade anhydrous sodium tripolyphosphate. They were mixed in a Hobart~mixer. This . produced a sticky mixture wlth a high tendency to cake.
:: It was then dried for approximately two hours in a 225 oven.

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A blender was used to break up the large granules. The partlcles were screened on a U.S. No. 12 sieve. The weight ratio of sodium tripolyphosphate to lemon juice solids was 1l.4;l exclusive of water of hydration. The starting concentrated lemon juice assays 4700 ppm ascorbate.

EX~PLE 5 A second mix was prepared with 454 grams concentrated lemon juice added to 2,270 grams anhydrous sodium tripoly-- phosphate. It was well mixed with a Hobart mixer and then dried overnight in a 104F~ oven. The large particles were then broken up in a blender and passed through a U.S. No. 12 sieve. The weight ratio of sodium tripolyphosphate to lemon juice solids is 11.4:1 exclusive of water of hydration.
The starting concentrated lemon juice assays 4700 ppm ascorbate.
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~ EXAMPLE 6 ., . ~ .
In this example, the treatment of salmon is described. The procedure followed was to flex salmon steaks with a pre-measured amount oE a treatment solution for thirty-five to forty-five seconds depending on the thickness of the steak.
The treatment solutions are listed in Table 3. The sodium tripolyphosphate/lemon ~uice composition used for all samples bearing the numbers 4 and 5 were prepared by the method o~ Example 5. In these samples, 3 to 6 ppm ascorbic acid plus 225 to 420 ppm citric acid were added to the treated salmon through the lemon juice. The re-sults of the tests are shown in Table III below.

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~L~S5~ 2 TABL~ t Treatment Solutions . ~
1 Sodium tripolyphosphate . 2 Sodium hexametaphosphate plus salt : 3 Sodium tri.polyphosphate plus erythorbate ; 4 So~ium tripolyphosphate/lemon ~:
: concentrate Mixture of sodium hexametaphosphate : -plus salt and sodium tripolyphosphate/ ~ : :
lemon concentrate ~ -~
6 Sodium tripolyphosphate plus erythorhate ~ ~ :
plus salt 7 Control ~ :
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ri ,D, ~:1 . r r~, : a. ~ ~
h ~;) ~ rO ` ~ O
:: O ~ Ir) ~d rrd ` rO q) Z; ~ ~¢ ~ S O Z I¢ ~ ~J . P~ : :
.'` P~. ~ Q ~ LO ~d E-l '~1 ~1 ~( . ~ O ~) ~) ~ ~1 ~ `
~i 5-1 O F. ~ l~ ~) ` ~ ~ QO
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r-J P.l E-l 1:~ ~4 Pl E~
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: 0.148 3.30 5.13 0.927 0.587 0.340 0.569 Tripoly , 0.396 1.62 8.97 0.842 0.587 0.255 0.372 Hexameta ~ 0.132 0.82 394.00 0.966 0.587 0.379 0.655 Tripoly : ~ 0.182 1.29 10.30 0.942 0.587 0.3`55 0.615 Tripoly ~ 0.264 0.82 `11.60 0~888 0.587 0.301- 0.481 Tripoly .` 0.479 0.65 186.00 0.881 0.587 0.294 0.509 Tripoly 0.132 2.55 12.80 0.587 0.587 0.148 2.31 7.70 0.881 0.625 0.256 0.442 Tripoly , , . . .
. 0.396 2.41 7.70 0.788 0.625 0.163 0.238`IIexameta , . .
0.115 1.63 250Ø 0.757 0.625 0.132 0.228 Tripoly 0.165 0.90 10.3 0.803 0.625 : 0.178 Q.308 Tripoly 0.264 1.18 8.97 0.904 0.625 0.279 0.446 Tripoly ... .
.~: 0.595 0.50 186.00 0.927 0.625 0.302 0.5:23 Tripoly ~:
: . 0.132 2.42 8.97 0.625 -- -- -- _-, ~, ':
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,--__ . .............. ~ __ , ......... .. _. ~_ Net Frozen Net Thaw Percent Cook ~i Icl Drip ~ -lC 220.0 21~ .9 O . S00 1~4.6 8~ .3 2C 190.8 190.0 0.420 161.2 ~5.0 3C 217.2 216.2 0.460 184.8 ~5.2 4C 249.2 248.3 o ,361 217.8 87.6 5C 224. ~ 224.0 0.355 195.2 87.3 6C 229.0 22~ .5 0.218 ].99. ~ 87.4 7C 213.1 20~ .5 ~ .04 170.0 83.3 lD 190.6 189.5 0.57g 157.5 83.0 2D 203.7 202.8 0.444 172.5 85.3 3D 222.0 220.9 0.495 187.9 85.0 4D 185.7 185.0 0.377 156.7 84.8 5D 217.2 216.8 0.184 185.9 85.8 6D 220.9 220.1 0.362 190.1 86.5 7D 240.9 230.0 4.54 193.6 ~4.0 . . _ , .~ . . ... ~ .' .
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: Sample Appearance Taste ~exture lC Very pale pink, some bland, not much improved over . lD yellow noticeable, bet:ter than 7 7 . almost as bad as 7 2C Very pale pink, some bland, not much improved over `2D yellow noticeable, be-t:ter than 7 7 almost as bad as 7 33D Light red, faded fa.-~r, better improved some somewhat when cooked than 1 and 2 over l and 2 4C Medium to dar~ red, second in -almost as good 4D - next in line to 6 preference to as 6 ` 6, lemon could : . . - be-detected 5C Light red, some almost same almost as good 5D fade whQn cooked as 4 as 6 ~ - 6C Best of series both best of series excellent -:. 6D before and after cook; --Dark red, very little some salt protein cooked out detected 7C Worst appearance oily ~nd bland poor, oily - 7D after thaw and cook; ~ ;
yellow, oily, white : - protein globs .
: NOTF.S: Salmon werë cooked in oven at 520F. for 15 minutes to an internal temperature of 162 F.

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EX:I'.MJ?LE 7 To demonstrate the operability of the instant invention with the inclusion of sodium erythorbate, and to show the benefits thereof, several compositions were made and tests run. The composltions were as follows:
- COMPOSITION I
:.
Thirty milliliters of concentrated lemon juice (63 percent water) were hand mixed with 100 grams anhydrous sod~um trlpolyphosphate. The weight ratio of sodium tripolyphosphate to lemon juice solids is 7.6:1 exclusive of water of hydration.

COMPOSITION II
~; A twenty percent solution of sodium erythorbate in concentrated lemon juice was prepared. Thirty milliliters of this solution were hand mixed with 100 grams of anhydrous . ~ . . . .
sodium tripolyphosphate. The weight ratio of sodium tripolyphosphate to lemon juice solids is 11.3~1 exclusive o~ water of hydration.

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~ COMPOSITION III
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A solution including 20 percent sodium erythorbate - was prepared using REALEMO~ natural strength lemon juiee.

Thirty milliliters of this solution were hand mixed with 100 grams of anhydrQus sodium tripolyphosphate. The weight ratio of sodium tripolyphosphate to lemon juice solids is 70:1 exclusive of water of hydration.

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Pork sausage was then prepared using the ahove compositions and their components in various amounts. The samples were refrigerated for various periods, as indicated in Table IV.

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R~NCIDITY DEVELOP~ NT IM REFRIGER~TED
FRES~I PORI~ SAUSAGF
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i TBA VALUE

~ Treatment_ ~ E~__ __@ll 4 day ~ Y__ 1 C5NTROL cooked __ 4.80 8.50 9 50 _ ,, _ ~ . .. _ ; 2 200 ppm cooked __ 5.00 19.50 17.00 i _ Erythorbate . ~ _ _ . _ _ _ .
3 0.5% Tripoly cooked __ 1.75 2.10 2.85 0.65% _ Co~position I cooked __ 1.50 1.80 2.45 5 0.65- _ `~
Composition II cooked __ 1.20 1.50 1.30 6 0.656 ~ ~ _ Composition III cooked __ 1.45 1.40 1.30 .. _ . .. ~ . _ ~ _ . _ . .
, .~ ~ _ _ ,_ . __ 7 CONTROL raw 5.85 1.80 4.70 7 30 .- .. ._ . . . . . __ 8 Er thorbate raw 5.90 1.35 5.95 7.50 . _ Y . __ ._ . _ . .__ 9 0.5% Tripoly raw h.25 0.85 1.40 1.40 -_ ~_ ~
~ Composition I raw 6.10 1.05 1.60 2.60 ., . ... _ _ .... _ _ ... _ .
11 0.656 raw 6 05 0.801 20 0 85 Composltion II . . .
. .. _ .. _ _ . . I
; 12 Compo~ltlon III raw 6.18 0.751.40 0.70 NOT~: A11 samples contained 80 grams ground pork, ~ 2 percent~NaCl and suf~icien-t water to make 100 grams.
-~ Thus, there may be included in the tripolyphosphate/
lemon juice comp~sitions of this invention up to about ~.o percent by weight of a compound selected from the group con-sisting of ascorbic acid, erythorbic-acid, and their sodium salts. It is preferred to use from about 2.5 percent to about 5.0 percent by weight based on the hydrated tripolyphosphate/
j; - lemon juice composition.

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Claims (3)

The subject matter which applicant regards as his invention is particularly pointed out and distinctly claimed as follows:

1. A meat treating composition comprising dry, free-flowing sodium tripolyphosphate hexahydrate in which the water of hydration contains lemon juice solids in an amount equivalent to one part by weight per 7 to 70 parts by weight of the sodium tripolyphosphate.

2. The method of making a meat treating com-position comprising dry, free-flowing sodium tripolyphos-phate hexahydrate wherein the water of hydration contains lemon juice solids which comprises hydrating anhydrous sodium tripolyphosphate with the equivalent of six moles of an aqueous solution containing 6 to 37 % by weight of lemon juice solids per mole of sodium tripolyphosphate.

3. The method of treating meat to maintain the color, taste and fresh quality thereof which comprises add-ing to such meat prior to cold or frozen storage from 0.2 to 0.6 % by weight of the meat of a dry, free-flowing sod-ium tripolyphosphate hexahydrate in which the water of hy-dration contains lemon juice solids in an amount equivalent to one part by weight per 7 to 70 parts by weight of the sodium tripolyphosphate.