"Anti-Oxidants - Pros and Cons"

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"Anti-Oxidants - Pros and Cons"

Post by Igor Duńczyk » Sat Sep 28, 2013 16:55

This topic is continued from the split topic: Seeking Sumac Sausages. at this link: http://wedlinydomowe.pl/en/viewtopic.ph ... sc&start=0
Hi Chuck !

I think this now calls for a new topic or thread on "Anti-Oxidants - Pros and Cons" or something in that vein as I sense a whiff of witch hunt regarding the use of sodium erythorbate in cured meats. I`mean: if somebody would force me to swollow either a teaspoon of pure sodium nitrite or a teaspoon of pure sodium erythorbate it wouldn´t take me too long to make up my mind.

Sodium erythorbate might be a chemical ingredient but so is salt - and everything can be harmful or even lethal. It´s just a matter of dosage. And you can leave out erythorbate - just as you can leave out cure, as long as you are aware what the consequences may be....

Personally I would NEVER EVER leave out neither:
Ascorbic Acid
Sodium Ascorbate or
Sodium Erythorbate
in any product made with the use of cure (sodium nitrite & potassium nitrate)
Because with the use of these anti-oxidants you reduce the healt hazard connected with possible residue of sodium nitrite that hasn´t been properly reduced to nitrogen oxide. It might be streching my point a bit too far if I claim that sodium erythorbate will save you from stomach cancer caused by nitrosamnes in products where these anti-oxidants were NOT used. But still.... Doesn´t it feel better to be on the safe side?

An important factor is always the practically applied dosis of an ingredient;
The average dosage of sodium ascorbate or erythorbate (the latter being a stereoisomer of sodium ascorbate) should not be higher than 0,06% pr. kg. cured meat. Which means that you will have to eat one kilogram of cured sausage to get half a gram of erythorbate into your body. The closest "natural" analogue of erythorbate is ascorbic acid of which the Tolerable Upper Intake Level in the US is 2.000 mg. And please know that with two grams of ascorbic acid (or erythorbate) you would ruin the nice red cure color alltogether :oops:

Also, if I had an assumption that a too high dosage of cure had been added to a product that was to cooked shortly after curing (frankfurters etc.) I would simply not allow the product to be made without adding max. dosage of one of the mentioned anti-oxidants.

So, my advice is: Start looking at the mentioned anti-oxidants as remedies that, in the best case, may contribute to save us from something far worse.

If chemical additives is an issue for any of you then you should look up standardized extract of Acerola berries (Malpighia emarginata) which can replace Ascorbic Acid / Sodium Ascorbate, but make sure how to handle the dosage level.

And remember: Ascorbic Acid is a NO GO (Skulls and crossbones) in any fermented meat product where it may get into direct contact with the cure (sodium nitrite).
For salamis and cured elements use ONLY sodium ascorbate or sodium erythorbate.
Last edited by Igor Duńczyk on Sat Sep 28, 2013 23:03, edited 1 time in total.
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Post by Igor Duńczyk » Sun Sep 29, 2013 00:20

Just to correct a spelling mistake:

The carcinogenic substance that may be formed from nitrite residue is called Nitrosamine
And it´s not because I want to scare the .... out of all who loves a crispy slice of bacon straight off the pan, but the formation of nitrosamines also takes place when you fry uncooked cured meats in oil/fat.
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Post by el Ducko » Sun Sep 29, 2013 03:13

Can we summarize some "rules" as to when ascorbic acid or sodium erythorbate should, or should not, be used? Also, why it would be used, main effects, possible side effects, recommended concentrations, limits...

I don't know about you, but I'm ignorant about the stuff, and also confused. Thanks for the help.
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Post by Igor Duńczyk » Sun Sep 29, 2013 23:30

Hi Duck-ooh :mrgreen:

Here are some of my "why´s"

We use cure in our meat products to counter the lethal dangers of a.o. Clostridium botulinum. Simultaneously we expose ourselves to the hazards of possible residue of sodium nitrite that may turn into the carcinogenic substance Nitrosamine, suspected to cause gastric cancer.

Anti-oxidants like Ascorbic Acid, Sodium Ascorbate or Sodium Erythorbate greatly reduces this hazard by speeding up the so called "reduction process" that "breaks down" sodium nitrite into the less dangerous nitrogen oxide during the curing process.

The reduction process will usually happen anyway, but at a lower speed and with less probability of a total breakdown of the sodium nitrite.
However, ascorbic acid and sodium ascorbate (and erythorbate) goes into a chemical interaction with the sodium nitrite thus facilitating the process and (as a very valued benefit) stabilizies the red "meat colour" which is obtained after the curing has taken place. The red myoglobin in the muscle tissue will remain in place instead of evaporating into thin air, like when you make a sausage with kitchen salt only.

By adding anti-oxidants the cured meat products simply maintains the red colour for a longer time without turning grey.

There are however certain limits for the addition of anti-oxidant addition, because their amount should be related to the amount of cure.
When using normal average cure dosage you should add 0,05% ascorbic acid or sodium ascorbate.
Or 0,06% sodium erythorbate which, because it has a lighter molecular structure, needs to be dosaged slightly higher :shock: (but it´s also much cheaper than sodium ascorbate).

But if you of some reason decide to use less cure than average, then the amount of anti-oxidant should be reduced proportionally. A. e. in Poland curing salt is most common and many use a blend of 50% curing salt and 50% kitchen salt if there is a high percentage of fat/lard in the product, so in this case the ascorbic acid or sodium ascorbate should equally be cut down to 0,03 or 0,025%.

So, when to use ascorbic acid or sodium ascorbate?
The acid (which is an chemical analogue to "vitamin C") is especially preferable in cooked sausages where you add the cure with salt and after a good kneading / blending add the asorbic acid towards the end of the blending process when the cure has been well distributed in the mass. This beause the asorbic acid must not get into direct physical contact with the sodium nitrite, or the chemical interaction will take place at breakneck speed, causing burnout and release of intoxicating gasses.

The sodium equivalent of ascorbic acid; sodium ascorbate and its analogue; sodium erythorbate are more safe in this respect as they work at a slower pace than the acid.
Thus making it less risky to add them to a meat blend where the cure has not been so thoroughly distributed, or less dissolved because of low Water Activity.
That is why sodium ascorbate and sodium erythorbate should always be used for salami or other slow cured meats such as raw hams or tenderloin.

Regarding cons when it comes to anti-oxidants I´m sorry - but I can´t spot them anywhere. Whereas I see potential trouble ahead for those who don´t use them.
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Post by redzed » Mon Sep 30, 2013 00:48

I spent a bit of time today trying to find a credible scientific study relating to sodium erythorbate but ended up with nothing. There are a number if sites that warn of the dangers of the additive and list the possible side effects. But after reading several, it appears that all have taken their information from the Livestrong website.
http://www.livestrong.com/article/34098 ... e-effects/

In looking at the Livestrong source, they cite an article from the Mayo Clinic that discusses side effects of high doses of Vitamin C. (Not specifically sodium erythorbate, although it is virtually identical to vitamin C, but does not have the same nutritional value).
http://www.mayoclinic.com/health/vitami ... ION=safety
There are also two other references, but they do not mention anything negative. So the Livestrong article on Sodium erythorbate is misleading and a bit of a sham.

At this point in my rudimentary research, I am led to believe that too much sodium erythorbate is the same as too much Vitamin C. But at the same time, I still would be interested in locating a study or analysis of this chemical.
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Post by el Ducko » Mon Sep 30, 2013 04:15

Being an old industrial guy, I look for the Material Safety Data Sheet first. Here's one: http://www.sciencelab.com/msds.php?msdsId=9924985 Looks like it's mostly an inhalation (dust) hazard.

Next, I look at what suppliers say. Here's one http://www.nuts.com/cookingbaking/salts ... n=2-Snacks which sells the stuff for about $5 a pound. They say "Sodium erythorbate is a food additive used predominantly in meats, poultry, and soft drinks. When used in processed meat such as hot dogs and beef sticks, it increases the rate at which nitrate reduces to nitric oxide, thus facilitating a faster cure and retaining the pink coloring. As an antioxidant structurally related to vitamin C, it helps improve flavor stability and prevents the formation of carcinogenic nitrosamines."

Note two items: (1) It is used with nitrates, but not with nitrites, and (2) as such, it helps prevent formation of nitrosamines. (This appears to be done via hastening the conversion to nitrite, reducing more rapidly the amount of nitrate available to react to form nitrosamines. ...but that's my speculation only.)

A note, here: this seems to conflict directly with some of Igor's statements above. Please comment.

Since most of our sausages (except the fermented ones) don't use cure #2, we wouldn't be interested in using sodium erythorbate anyway. I seem to recall that nitrosamine concern is about meats subjected to high temperatures, such as bacon frying. Cure #2 is not permitted in bacon curing for that reason.

The reason that the topic of sodium erythorbate came up was a discussion of making the cured, fermented sausage sujuk (spelled several ways). Most of the recipes that I've found don't use any cure whatsoever, which is dangerous but, considering the sources (ancient, traditional, Armenian/Turkish/Lebanese), that's to be expected. Len Poli lists three recipes, passed on to him by an Australian contributor whose last name might be Armenian. Len adds a note that calls for cure #2 in one recipe. In the other two, a note calls for cure #1. None call for ascorbic acid or sodium erythorbate, although there's probably some naturally occurring in the pomegranate juice. (It's a traditional [delicious] Turkish additive. We won't count that.)

My own personal thought- - I don't make fermented recipes, so there's no need for me to use cure #2 or ascorbic acid or sodium erythorbate. However, when I do get into fermented sausages, chances are very high that I won't use ascorbic acid or sodium erythorbate unless it's in the recipe.

...but let's keep talking about it. Is anyone out there using it in a recipe at the moment? ...better still, does anyone have a PUBLISHED recipe that calls for it? There are bound to be some, but I confess that I haven't looked very hard.

Thanks for the continued interest.
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Post by redzed » Mon Sep 30, 2013 06:15

el Ducko wrote:Note two items: (1) It is used with nitrates, but not with nitrites
The "nuts" website appears to be only half right. From what I have read it is used with nitrates and nitrites, in order to accelerate the conversion of nitrites to nitric oxide. And since my last post I found this:

http://www.accessdata.fda.gov/scripts/f ... ing&id=294

As far as "published" recipes using the additive, so far I have found it only in some of Poli's formulations. But of course it appears that it is widely used in commercial products.
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Post by Igor Duńczyk » Mon Sep 30, 2013 08:30

el Ducko[i] wrote:"...it increases the rate at which nitrate reduces to nitric oxide, thus facilitating a faster cure and retaining the pink coloring. As an antioxidant structurally related to vitamin C, it helps improve flavor stability and prevents the formation of carcinogenic nitrosamines."[/i]

Always pleasant to see ones own statements confirmed by other (more credible) authorities :mrgreen:

A note, here: this seems to conflict directly with some of Igor's statements above. Please comment.

I´m sorry Ducko - but I´dont quite catch the nature of the conflict (?)

Personally I would not leave out anti-oxidants when using either cure #1 nor #2.
After all, nitrate is always reduced into nitrite, just as nitrite during the curing process will generate a "pool" of nitrate. Which is why some pro´s claim that objectively speaking there is no need use a cure consisting of both nitrite and nitrate (cure #2) as the nitrite alone will provide sufficient amounts of nitrate when the curing takes place.
I will refrain from assessing if there is a "wrong or right" on this issue. You may consult the internet.

You should be aware that the staphyloccoccus in starter culture (and those present in nature) also contribute significantly to the reduction process.
However when using a very fast fast starter culture there won´t be time enough for the nitrate reduction and that is why cure #2 should not be used in this instance!

As for hazards connected with overdozing anti-oxidants I can only re-quote what I mentioned earlier: If you use a higher dosage than 0,05% ascorbic acid or sodium ascorbate (or 0,06% sodium erythorbate) you will topple the amount relation between the nitrite/nitrate and the anti-oxidant. This may lead to uneven colouring of the meat with possible brownish spots or areas :neutral:

One reason why so many recipes adressed to hobby sausage makers leave out the anti-oxidants is probably because most of these authors consider it less important to have color stability in quickly consumed home made products, whereas it is an imminent issue in commercial products because they have to present themselves nicely for weeks :wink:

And as is the case of the Sujuk (an interesting topic - I personally love that sausage taste :razz:) you´re perfectly right that acient recipes knew neither of cure nor anti-oxidants, and exactly the same goes for many of the (polish) recipes on this site which were conceived before the positive effects of anti-oxidants were known and understood.

Now as we know better I simply don´t understand why present day authors of recipes for hobby-sausage makers still leave out anti-oxidants when it has been established as a common fact that they contribute significantly to reduce the possible hazards of nitrosamines.
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Post by redzed » Mon Sep 30, 2013 21:33

Igor Duńczyk wrote:Now as we know better I simply don´t understand why present day authors of recipes for hobby-sausage makers still leave out anti-oxidants when it has been established as a common fact that they contribute significantly to reduce the possible hazards of nitrosamines.
Igor, two reasons come to mind:

1. One of the main reasons that many get into this hobby is to recreate traditional products without the modern ingredients and compounds used by commercial producers. You will see that especially on the Polish site of WD. The recipes there and the sausages shown by the forum participants mostly contain the basic ingredients and differ only in the methodology used in creating them. There is a trend out there of people rejecting the homogenized and over processed supermarket products loaded with 30 or more ingredients.

2. A large number of hobbyists probably don't own a scale that can weigh less than an ounce, never mind a fraction of a gram. Many still work with spoon measurements. (I purchased a scale that measures in tenths of a gram at a hydroponics store. I think most of their customers buy these scales if they deal in drugs)
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Post by el Ducko » Tue Oct 01, 2013 16:08

Igor,

..further thoughts on cure #1 vs. cure #2 and the role of antioxidant. I apologize in advance for being long-winded.

First, let's clear up a fundamental item. The writeup for cure #2 at Sausagemaker website http://www.sausagemaker.com/10108instacure24oz.aspx says, in part:
"...a cure specifically formulated to be used for making dry cured products such as pepperoni, hard salami, genoa salami, proscuitti hams, dried farmers sausage, capicola and more. These are products that do not require cooking, smoking, or refrigeration. Insta Cure™ No. 2 can be compared to the time release capsules used for colds--the sodium nitrate breaks down to sodium nitrite and then to nitric oxide [actually nitrous oxide, N2O] to cure the meat over an extended period of time. Some meats require curing for up to 6 months. InstaCure #2 contains salt, sodium nitrite (6.25%) and sodium nitrate (1%)."
So, please note that Cure #2 contains BOTH nitrite and nitrate. In this formulation, cure #2 is equivalent to cure #1 plus 1% nitrate. Also note their statement that the reaction goes from nitrate to nitrite, and is rate-limited, not equilibrium-limited.

As to
"nitrite during the curing process will generate a `pool` of nitrate,"
this assumes that the reactions are reversible and that some sort of equilibrium is reached. However, sodium erythorbate is described as an accelerant, which implies a forward reaction rate. Only if the nitrate and nitrite were close to being in equilibrium would there be an appreciable amount of nitrate generated by the reverse reaction.

What you are probably referring to when you speak of a "pool" is the case of several reactions in series. (I`m much more current on this, having worked on chemical process simulations for much of my engineering career.) Nitrate produces nitrite, which produces nitrous oxide, which is consumed. Here is a reaction scheme, as diagrammed at http://en.wikipedia.org/wiki/Nitrite

Nitrate-goes to nitrite:
. . . . . . . . .NO3- + 3H+ + 2e <-> HNO2 + H2O

Nitrite then generates nitrous oxide by a series of steps:
. . . . . . . . .2HNO2+ 4H+ + 4e <-> H2N2O2 + 2H2O
. . . . . . . . .N2O4 + 2H+ + 2e <-> 2HNO2
. . . . . . . . .2HNO2+ 4H+ + 4e <-> N2O + 3H2O
...which is what reacts with the myoglobin, as we are often told. Indeed, these are shown as reversible reactions. However, because N2O is consumed, everything flows to the right, the nitrate being consumed to maintain the supply of nitrite or, if there is no nitrate present, the nitrite is consumed preferentially to produce N2O as it is consumed.

If you look up the Wikipedia writeup, you`ll see so-called "reduction potentials" listed. Fortunately for our readers, my last thermo course was over forty years ago, so probably neither of us should go there. Let`s just say that it`s possible to drive the reverse reactions, but only at considerable cost of energy. What's more important is that product N2O is being consumed, driving the reactions to the right.

If you start with nitrate only and the reactions proceed, a pool of nitrite (not nitrate) will build up, but only enough that the rate of nitrite production equals the rate of nitrite consumption. (If you start with both nitrate AND nitrite, the pool is already there.) As the nitrate starting material is consumed, the reaction rate to nitrite drops because concentration drops. The nitrite intermediate continues to react to the final N2O product, but the concentration of intermediate falls, reducing its rate.

The net result is that a pool of intermediate nitrite grows, stabilizes, then declines. In this case, where final product is all consumed, both the nitrate and the nitrite concentrations go essentially to zero too.

To generate a pool of nitrate, the nitrate-nitrite reaction would have to run in reverse. The reduction potentials suggest that the reverse rates are pretty slow. Yes, it IS possible, but not worth arguing over. (Don`t let me get into lecture mode!) Whether or not there is a pool of nitrate generated, please accept that, in a series of reactions where the product is removed, eventually the starting material and all intermediates will also be consumed.

You mentioned:
"However when using a very fast fast starter culture there won´t be time enough for the nitrate reduction and that is why cure #2 should not be used in this instance!"
I believe you are correct. All the recipes that I have seen agree with you. The fast reactions get the sausage into conditions hostile to further bacterial growth, so nitrate protection is no longer necessary. (However, nitrite protection IS necessary during that short period of time when the "good" bacteria dominate and do their work. This is why cure #2 contains both nitrate and nitrite.) Note that this is a rate-governed reaction, not an equilibrium condition. This suggests that the reaction of nitrate to nitrite is (under the conditions where we operate) irreversible.

You also mentioned:
"topple the amount relation between the nitrite/nitrate and the anti-oxidant"
I`m not sure what you mean, here. The anti-oxidant accelerates conversion of nitrate to nitrite, and if the mixture is not uniform, pockets of high nitrite might well occur. Best advice from both you and me about adding too much: "Don`t do that!" (Follow the directions.)

I apologize for my long-winded, obscure chemical logic. It`s a case of "too much education without a helmet" perhaps. (...or perhaps Chuckwagon's style is rubbing off on me? Aarrgghh!) Unlike Chuckwagon, though, I have difficulty explaining these things to the general public. Perhaps we should have done this off-line, so as not to make our forum members dizzy.

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Post by ssorllih » Tue Oct 01, 2013 17:59

I had no difficulty following that. AND I wondered about the nitrite to nitrate reaction but am not knowledgeable enough to present an argument.
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Post by redzed » Tue Oct 01, 2013 23:18

Thanks for that analysis Duckie. Your technical knowledge and analytical skills are appreciated. You are a definite asset to this forum.
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Post by Igor Duńczyk » Wed Oct 02, 2013 13:47

Ducko - I´m not ashamed to admit that you´ve got the upper hand when it comes to chemical insight and how to make long-winded, obscure chemical logic accessible to a broader public. One reason why I opened this debate is that I think everybody on this forum ought to ask themselves "why" and "how does it work" when dealing with chemical components.
So the more who read your long-winded posting the better :mrgreen:

Concerning the nitrite/nitrate topic I stated "...some pro´s claim that objectively speaking there is no need use a cure consisting of both nitrite and nitrate (cure #2) as the nitrite alone will provide sufficient amounts of nitrate when the curing takes place. I will refrain from assessing if there is a "wrong or right" on this issue..."

By this I mean (without going into the chemical facts) that you will find professionals of the trade who will maintain the point of view, that addition of nitrate in cure for salami production is not a strict necessesity.

When looking at commercial salami production you will find a very diversified picture in Europe where the vast majority of producers south of the Alps will use a cure #2 combination, whereas many large German salami producers use only cure #1 and to the best of my knowlegde the outcome of their curing seems no way to be less accomplished.

In the Central- and European countries salami curing by nitrite alone is also close to being the rule.

Now turning the picture 180 degrees: If you for the sake of "the less E-numbers the better" wants to cure without nitrite but as alternative picks one of the "organic" solitions composed of a.e. hydrolized sellery juice or beta vulgaris (Chard or Swiss Chard) juice, you do so because these juices are rich in (natural) nitrate. Which during the curing process is reduced to nitrite and to promote the nitrate reductase activity you will need a culture with a strong concentration of staphyloccoccus.

But then again (returning to my previous point why only cure #1 should be used together with fast starter cultures) the staphyloccoccus will be inactivated when pH gets below 5.0 - so with a too quick pH drop there will be too little time for the biological part of the reduction process to take place. That´s also why fast cultures and high nitrate concentration is a bad combination.

As for my statement on an "amount relation" between nitrite/nitrate and anti-oxidant I admit that this also calls for some lengthy chemical logic (anybody reading this: Feel free to deliver the explanation :o ) but for sure this relation sets a limit to how much anti-oxidant can be applied without toppling the balance.
I stress this because some may think "the more the better" because after all - we don´t have anything against vitamin-C or....? :wink:
But please don´t cross the 0,05% borderline when it comes to adding it into cured meats! I´ve seen enough miscoloured hams in my time because some wise-guy technologist tripled the amount of sodium ascorbate assuming "the more the better" Well, not in this case :???:


Red - I fully agree that there is no need to stuff homemade delicaties with E-numbers, but equally shake my head at the blindfoldedness that some people exhibit and automatically thinks in terms of "Food poison" whenever they spot an E-number on a declaration label. And personally I think it´s a pity if the mentioned anti-oxidants should fall victims to this misconception. In such small dosage they do more good than evil.
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Post by el Ducko » Wed Oct 02, 2013 23:40

Igor,

Looks like we agree, especially about "more is better" being wrong. (I figured that we did agree, but wasn't sure.)

Thanks especially for providing a view into European practice. Too often, we in the USA either are not able to see the practices of other countries, or else don't bother to look. The real strength of Wedliny Domowe is that it exposes us in the English-speaking world to traditional European practice.

For that, I thank you, and also thank all who visit and contribute to the website content.
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Post by redzed » Thu Oct 03, 2013 06:06

Ditto to the above. Your expertise and knowledge are appreciated Igor. And I admire that you take the time to reply with such thoroughness. The points about using cure 1 with fast acting cultures are especially interesting and I might give it a go with my next project. :grin:
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